JP2023506619A - Preparation from Germanosilicate CIT-14/IST and Germanosilicate CIT-13/OH - Google Patents

Abstract

The present disclosure relates to macroporous germanosilicate compositions designated CIT-13/OH and CIT-14/IST, the two macroporous germanosilicates comprising 10- and 14-membered ring channels and 8 It has a three-dimensional scaffold with membered and 12-membered ring channels, respectively. This disclosure also shows how to transform the former into the latter under conditions consistent with the inverse sigma transformation. Also disclosed is the use of macroporous germanosilicate compositions.

Description

Cross-reference to related applications

This application claims priority from US Provisional Patent Application No. 62/947,434 filed December 12, 2019, the contents of which are incorporated by reference for all purposes.

public authority

none

The present disclosure is directed to germanosilicates designated CIT-13/OH and CIT-14, and the conversion of the former to the latter by inverse sigma transformation.

Zeolites play an important role as heterogeneous catalysts and are used in various industrial situations. Initially, these materials were developed primarily to assist the petroleum industry in its quest to create more selective and robust catalysts for making gasoline and other fuels. These solids are now emerging as specialty materials for specific large-scale applications due to their structural and chemical composition-based properties. A great deal of effort is required from the discovery of new materials to their practical application, but there is still room for the discovery of new structures that surpass existing materials.

One goal for finding new materials is the hope that increasingly large pores that retain some catalytic properties on their inner surface will be able to handle larger feed molecules in the field of petroleum upgrades. is.

Therefore, there remains interest in finding new crystalline phases for use in these applications. This research aims to address deficiencies in the technology in this area.

Synthetic molecular sieves typically contain inorganic (Na+, K+, etc.) and organic structure directing agents (OSDA), mineralizers (OH- or F-), heteroatoms (Al, B, Ge , Ti, Sn, etc.) are prepared using hydrothermal synthesis. The synthesis of crystalline molecular sieves is complicated. Some parts of the recipe and assembly process have been designed, but it is difficult to predict the outcome of that approach.

Topotactic conversion of existing zeolites has played a role as a method to prepare new zeolite frameworks that could not be synthesized by conventional hydrothermal methods. A typical example is the assembly-disassembly-assembly-reassembly ( ADOR) strategy and these transformations are shown schematically in Figure 1. are shown in 1(A) and 1(B), respectively.

CIT-13 (*CTH: asterisk (*) indicates structural disorder), which has an ultra-large pore structure with 14MR and 10MR channels, was discovered in the process of investigating the function of imidazolium compounds with benzyl groups as OSDA. was done. Isostructure germanosilicates, NUD-2 and SAZ-1, crystallized from imidazolium-based OSDA and fluorine-based gels have also been reported. CIT-13 is a structure in which a Si-rich cfi layer is bridged by a two-dimensional array of Ge-rich d4r units. The structure of the cfi layer gives the d4r unit two crystallographically equivalent positions. This equivalence was revealed by perturbation of the d4r unit position in the CIT-13 framework and conversion of *CTH to CFI (Fig. 1(C)). Most importantly, the structure of CIT-13 resembles that of IM-12, showing the rich chemistry of the germanosilicate modification.

We previously reported the similarity between *CTH and UTL, novel frameworks CIT-14 and CIT-15 with prepared 2D 12/8MR and 1D 10MR channel systems based on ADOR transformations, respectively. disclosed two. However, ADOR products of sufficient quality for Rietveld purification by powder X-ray diffraction (PXRD) have never been prepared. This is believed to be due to the possible presence of Si-O-Si connectivity within the interlayer region, which causes incomplete delamination. Liu et al. reported that a weak base solution such as ammonium hydroxide dissociates the inter-layer Si-O-Si bonds that prevent complete exfoliation of the CFI-type layer of CIT-13, resulting in a structure called ECNU-21 (CIT-15 and isostructure). reported to have been obtained. We also found that in the germanosilicate Ge-CIT-5, which has a dzc (double zigzag chain) composite building unit in place of the d4r unit, a weak base solution exfoliates the CFI-type layer. Most recently, the formation of partially demanganized ECNU-23 (same structure as CIT-14) from the d4r unit of CIT-13 and its structural solution (based on electron diffraction) have also been reported. This synthesis was similar to the inverse sigma transformation of IM-12. However, due to the unique germanium sequence within the d4r unit of CIT-13, inverse sigma conversion by leaching the pure Ge-4-ring with strong acid has not been previously reported.

The present disclosure describes recently reported crystalline microporous jars with CIT-13 topology prepared by the fluoride-free hydroxide route, as described in U.S. Pat. No. 10,828,625. It is directed to new germanosilicates obtained from manosilicates. This document is hereby incorporated by reference in its entirety for all purposes including characterization of materials of CIT-13 topology and methods of making and using. These CIT-13 germanosilicates are hydrothermally prepared using benzylimidazolium organic structure directing agents and are characterized by having a three-dimensional framework with pores defined by 10- and 14-membered rings. (with pore sizes of 6.2×4.5 Å and 9.1×7.2 Å, respectively). This is the first known crystalline silicate with such a structure. These structures were characterized by powder X-ray diffraction (PXRD) patterns, unit cell parameters, SEM micrographs, ²⁹ SiMAS NMR spectroscopy and adsorption-desorption isotherms.

This disclosure describes a germanium-containing, ultra-large pore molecular sieve CIT-13 synthesized without the use of fluoride. After removing the clogged organics, the CIT-13 obtained from the fluoride-free preparation shows a difference from the CIT-13 sample prepared in the presence of fluoride. CIT-13 prepared by a fluoride-free method undergoes an inverse sigma transition, yielding CIT-14 with no mesopores. 13 was found to transform into a CIT-5 type germanosilicate much faster than 13. Rietveld structural analysis of CIT-14 confirmed that it has 12- and 8-membered ring channels, but the unit call parameters of this material were slightly different from those previously reported. ¹⁹ F magic angle spinning (MAS) and 1H-29 cycloparalized (CP) MAS nuclear magnetic resonance (NMR) spectroscopy results in CIT-13 crystallized without fluoride synthesized in the presence of fluoride. It became clear that it has a germanium position different from that of CIT-13.

The present disclosure is further directed to methods for engineering the structure of these CIT-13 germanosilicates prepared by the fluoride-free hydroxide route. The Si/Ge ratio ranges from 3.8 to 10 and the material is manipulated by exposure to heat and steam under suitable reaction conditions to effect inverse sigma conversion. This mechanism for this material is hitherto unknown. The present disclosure is also directed to the germanosilicate CIT-14 product resulting from such manipulations. The germanosilicate CIT-14 was previously disclosed in U.S. Pat. No. 10,293,33, the contents of which are hereby incorporated by reference for all purposes, or at least for methods of preparation and characterization of CIT-14. , was accessible by an ADOR transformation of the phyllosilicate designated CIT-13P (ASSY-DISASASSEMBLY-Organization-Re-ASCEMBLE).

Certain embodiments of the present disclosure include those crystalline microporous germanosilicate compositions, designated CIT-14/IST, with 8- and 12-membered ring channels. The CIT-14/IST composition, in some embodiments, is Characterized by a powder XRD pattern with at least 5, 7 or 10 characteristic peaks at 0.5, and 27.69±0.5 degrees 2-theta. The present disclosure also provides a more complete disclosure of the different uncertainties associated with the peaks, the full range of characteristic peaks, and the relative intensities and selection of peaks that characterize these materials.

CIT-14/IST compositions, in some embodiments, have a Si:Ge ratio of from 12:1 to 20:1, or from 14:1 to 18:1, or any subrange within these ranges. characterized by being in

The CIT-14/IST composition is, in some embodiments, according to claims 1-4, characterized in that the crystals are orthorhombic. In some embodiments, the CIT-14/IST crystal has a Cmmm space group, or a Cmcm space group, or an intracrystalline disorder of the two domains. In some embodiments, the crystalline microporous germanosilicate CIT-14/IST composition has unit cell parameters according to:

[Table 1]

In some embodiments, the 8-membered ring channel has a CIT-14/IST composition pore size of about 3.3 Å x 3.9 Å and the 12-membered ring channel has a pore size of about 4.9 Å x 6.4 Å. . Physical strain (eg, compression) or the Si:Ge ratio may change these values.

In some embodiments, the crystalline microporous germanosilicate CIT-14/IST composition is or is derived from the inverse sigma transformation of a crystalline microporous germanosilicate designated CIT-13/OH. It is possible. In some embodiments, the crystalline microporous germanosilicate CIT-14/IST composition is sufficient to degarment the CIT-13/OH germanosilicate to form a "-CIT-14" composition. It is derived from or derived from a crystalline microporous germanosilicate designated CIT-13/OH by exposure to concentrated aqueous mineral or other strong aqueous acid conditions at elevated temperatures for a period of time. Isolating this as-formed "-CIT-14" germanosilicate and calcining to form a crystalline microporous germanosilicate CIT-14/IST composition. Exemplary conditions for effectively performing these transformations are described elsewhere in this disclosure.

The specific morphology, properties, and manufacturing conditions of the crystalline microporous CIT-13/OH germanosilicates are more clearly defined in this disclosure, but these compositions are free of fluoride ions and It needs to be manufactured within a certain Si:Ge ratio range. The synthesis of these CIT-13/OH germanosilicates is conveniently carried out using the specific substituted benzylimidazolium organic structure director (OSDA) cations defined herein. In some preferred embodiments, the precursor CIT-13/OH germanosilicate is fluoride-free and has at least, preferably d4r units with an average of 4 or more Ge atoms, wherein Ge- 4 - Allows for the presence of rings.

In other embodiments, the crystalline microporous germanosilicate CIT-14/IST composition comprises at least one alkali metal salt, alkaline earth metal cation salt, transition metal, transition metal oxide, transition metal salt, or containing a micropore comprising a combination of

In other embodiments, the crystalline microporous germanosilicates CIT-14/IST, either in their acid or metal contaminant form, are used as catalysts or in processes within the scope defined elsewhere herein. Used as an adsorbent.

The present disclosure also includes other embodiments directed to the preparation of the crystalline microporous germanosilicate CIT-14/IST, where the crystalline microporous germanosilicate CIT-13/OH Also included are those methods comprising contacting with a concentrated strong aqueous mineral acid at an elevated temperature for a time sufficient to convert to the CIT-14 composition. The present disclosure also encompasses pre-baked, as-is "-CIT-14" compositions.

The disclosure also encompasses those embodiments of CIT-13/OH germanosilicates prepared by the hydroxide route as specifically described herein. The present disclosure also provides CIT-13/OH characterized as having d4r units containing an average of at least, preferably 4 or more Ge atoms per d4r, allowing for the presence of Ge-4-rings in the d4r units. Also included are those embodiments of germanosilicates. The present disclosure also encompasses those embodiments of CIT-13/OH germanosilicates that exhibit previously unobserved reactivity characteristics that are the result of the new and unique physical characteristics defined herein. do.

The patent or application file contains at least one drawing/photograph executed in color. Copies of this patent or patent application publication with color drawings/photographs will be provided by the United States Patent Office upon request and payment of the necessary fee.

The present application will be better understood when read in conjunction with the accompanying drawings. For purposes of explaining the subject matter, the drawings depict exemplary embodiments of the subject matter, however, the presently disclosed subject matter is not limited to the particular methods, apparatus, and systems disclosed. do not have. Additionally, the drawings are not necessarily drawn to scale.

Figure 1 (A-C) provides a schematic illustration of known germanosilicates. do the conversion. Fig. 1(A) inverse sigma transform, Fig. 1(B) ADOR transform, Fig. 1(C) diffusionless rearrangement of d4r array (*CTH → CFI transform). *The CTH-type skeleton is displayed as the base material of the model. Figure 2 is a schematic representation of the studies conducted and reported herein. FIG. 3 shows CIT-14/ESP (ESP stands for ethoxysilylated pillar. 3(A-B) shows its theoretical PXRD data (FIG. 3(A)) described in US Pat. No. 10,293,33. ) and pore channel dimensions (FIG. 3(B)). Figure 4(A-B) shows the CIT-14/ SEM images of IST samples are shown. Figure 5 (A-C) are SEM images of the CIT-13/OH samples. CIT-13/OH [3.71] (Fig. 5(A)); CIT-13/OH [3.56] (Fig. 5(A)), and CIT-13/OH [4.33] (Fig. 5(C)). Figure 6 shows the ¹ H- ¹³ C 8 kHz CPMAS spectra of the asmade versions of CIT-13/OH[4.33], CIT-13/F[4.33] and 1,2-dimethyl-3-(3-methyl ^13C solution spectrum of benzyl)imidazolium chloride. FIG. Figure 7 shows the ¹ H- ²⁹ Si 8 kHz CPMAS spectrum of the off-the-shelf version of CIT-13/OH[4.33]. FIG. 8 (A to G) are diagrams showing the results of characterization of CIT-13. Figure 8(A): Two OSDAs capable of crystallizing CIT-13 without a fluoride mineralizer. Figure 8(B) 8(B-E). PXRD patterns of selected examples of CIT-13/OH samples. (b) As-made and FIG. 8(C): calcined CIT-13/OH [3.88], FIG. 8(D): as-made and FIG. 8(E): calcined CIT-13/OH [4.33]. Figure 8(F): PXRD profile of reference CIT-13/F with Si/Ge~5. Figure 8(G): Ar adsorption isotherms (logarithmic scale) for CIT-13/OH[3.56] and CIT-13/F[4.18]. FIG. 9(A-K) show the PXRD patterns of the as-prepared CIT-13/OH samples compared to those of the reference CIT-13/F with Si/Ge=˜5. 9(C): Batch #5, Figure 9(D): Batch #7, Figure 9(E): Batch #8, Figure 9(F): Batch #12, Figure 9(G): Batch #13, Figure 9(H): Batch #15, FIG. 9(I): Batch #16, FIG. 9(J): Batch #17, and FIG. 9(K): Batch #18. FIG. 10 shows the PXRD patterns of the as-prepared CIT-13/OH sample and its refluorinated version. (310) diffraction is emphasized Figure 11 (A-E) shows the structural changes during conversion of *CTH to CFI observed based on PXRD profiles. PXRD profiles of calcined CIT-13/OH[4.33] (FIGs.11(A-B)) and CIT-13/OH[3.88] (Figs.11(C-D)). 11(C-D)) were measured in the range of (a, c) 4-40° and (b, d) 5-9° after 10 days of exposure to atmospheric humidity. Changes in the d200 interlayer distance of CIT-13/OH[4.33] compared to CIT-13/F[4.31] (Fig. 11(E)). Figure 12 shows the ²⁹ Si 8 kHz MAS spectra of calcined CIT-13/OH[3.88] and Ge-CIT-5 prepared therefrom. ²⁹ SiMAS NMR is qualitatively identical to that of CIT-14/ESP germanosilicate prepared by the ADOR synthesis described in US Pat. No. 10,293,33, with minor ^Q Si species and Multiple Q ⁴ Si environments within the -120 chemical shift region are shown. Figure 13(A-B) shows the inverse sigma transformation of CIT-13 to CIT-14. Schematic representation of the inverse sigma transformation of CIT-13/OH leading to CIT-14/IST (Fig. 13(A)); ). Figures 14(A-B) show the PXRD profiles of the parent CIT-13 sample (black), the 12M HCl fresh material (fuchsia), and the calcined sample (blue). PXRD profiles of CIT-13/F[3.87] (FIG. 14(A)) and CIT-13/OH[4.33] (FIG. 14(B)). Figure 15 shows the PXRD profiles of CIT-14/IST from CIT-13/OH [3.56] (top), CIT-13/F [4.33] (middle) and (a) 4-40°, (b) 6-10°, (c) The theoretical model of 'chaotic' CIT-14 optimized based on the GULP algorithm in the range 10.0-12.5°. (d) ²⁹ SiNMR spectra of CIT-14/IST and CIT-14/ESP samples. (The SiMAS spectrum of ²⁹ CIT-14/ESP is taken from US patent application Publ. FIG. 16 shows the effect of elemental composition on the intensity of the PXRD peaks of CIT-14. a) seven T sites in CIT-14 and germanium at (b) T1, (c) T2, (d) T3, (e) T4, (f) T5, (g) T6 and (h) T7 sites Simulated PXRD profiles of the CIT-14 framework at 0 (black), 10 (cyan) and 20 (red) are shown. Peak-1, Peak-2 and Peak-3 represent (110), (200) and (001) diffraction, respectively. Figure 17(A) shows the experimental design and PXRD patterns in the range of 4-40° (Figure 17(B)) and 6-9° (Figure 17(C)) for the resulting CIT-14/ESP samples. ing. 18 (A-D) in Fig. 18 are IM-12 [3.80] (Fig. 18 (A)), IM-12 [4.79] (Fig. 18 (B)), COK-14 from IM-12 [3.80] (Fig. 18 (C)), SEM image of COK-14 from IM-12 [4.79] (Fig. 18(D)). Figure 19 shows the PXRD profile of COK-14 from IM-12 [3.80] and COK-14 from IM-12 [4.79]. Figure 20(A-B) show the Ar-adsorption and desorption isotherms of the parent CIT-13/OH, CIT-14/IST and CIT-14/ESP on: linear scale (Figure 20(A)) and logarithmic scale (Figure 20(A)). 20(B)). Figure 21 (A-D) shows the results of structural analysis of CIT-14/IST. (Fig. 21(A)) Observed profile (top), calculated profile (middle), difference profile (bottom) in the Rietveld refinement of CIT-14. (FIG. 21(B)) Projection along the crystallographic principal axes [001], [010], [100] of CIT-14 (3×3×3 unit cell). (Fig.21(C)) Two-dimensional 12-8-ring channel system in the idealized structure of CIT-14. (FIG. 21(D)) Schematic diagram showing the disorder of CIT-14. FIG. 22(A) shows the idealized structure of CIT-14/IST. Silicon atoms, germanium atoms, and oxygen atoms are shown in blue, green, and red, respectively. Figure 22 (B-C) show the pore sizes of the 12- and 8-membered rings of CIT-14/IST, respectively. Figure 23(AC) shows ¹⁹ F12kMAS NMR spectra: ready-made CIT-13/F [4.33], fluorinated CIT-13/OH [4.33] (fig 23(B)) and fluorinated CIT-13/OH [3.56]. (fig23(C)).(Aterisks (*) indicate spinning sidebands on the fluorinated silica (19F-Si) surface formed as a result of fluorination with ammonium fluoride). FIG. 24(AC) shows ¹ H- ²⁹ SiCPMAS spectra of water demanganized CIT-13/OH, CIT-13/F, and IM-12 samples with different germanium contents. The parent germanosilicate sample and its acid-leached products are shown on the left and right sides of the spectrum, respectively. FIG. 25 is a schematic showing possible germanium arrangements within the d4r unit. (Green balls and silver nodes indicate germanium and silicon sites, respectively (not all possibilities shown).

Detailed Description of Illustrative Embodiments

The present disclosure is directed to novel compositions of matter comprising crystalline microporous germanosilicates and methods of making and using these compositions.

Herein is disclosed a new synthesis method for *CTH-type germanosilicate molecular sieves without the use of fluoride. Removal of fluoride from the synthesis narrows the previously reported compositional window for crystallization of CIT-13 and slows the crystallization time. However, CIT-13 prepared from hydroxide media (CIT-13/OH) exhibits interesting properties that cannot be achieved with CIT-13 synthesized in the presence of fluoride (CIT-13/F). Fluoride-free CIT-13/OH is converted to CFI-type germanosilicate (Ge-CIT-5) by exposure to ambient humidity after calcination and from fluoride-containing gels with similar Si/Ge ratios. changes much faster than the conventional CIT-13/F. Also, CIT-13/OH, obtained by the fluoride-free route, can undergo an inverse sigma conversion to another scaffold, CIT-14, with 12MR and 8MR cyclic channels upon contact with a strong acid. . CIT-14 obtained by inverse sigma transformation (CIT-14/ist) did not exhibit the mesoporosity present in isostructural analogues obtained by ADOR-type transformation. Since these transformations are based on the presence and arrangement of germanium sites within the d4r unit, the presence of fluoride anions in the synthesis mixture influences the elemental (Ge and Si) composition and arrangement within the d4r unit of CIT-13. It can be concluded that These results also support Ge–O–Ge bonds and germanium tetracycles within the d4r unit of CIT-13/OH synthesized from a hydroxide-based gel, similar to that observed in IM-12. indirectly confirms its existence. Figure 2 summarizes the studies reported in this disclosure.

The present disclosure may be more readily understood by reference to the following description taken in connection with the accompanying figures and examples, all forming part of the present disclosure. The disclosure is not limited to the specific products, methods, conditions, or parameters described or illustrated herein, and the terminology used herein is for the purpose of illustratively describing the particular embodiments and is not intended to limit the disclosure of any claim. Similarly, unless otherwise stated, any description of possible mechanisms or modes of action or reasons for improvement is intended to be exemplary only, and the disclosure herein does not constitute any such implied mechanism. Or, it is not bound by the correctness of the mode of action or the reason for improvement. It is recognized that throughout this text the description refers to compositions and methods of making and using said compositions. That is, where this disclosure describes or claims features or embodiments relating to the compositions or methods of making or using the compositions, such descriptions or claims do not include those features or embodiments in their context. (ie, compositions, methods of manufacture, and methods of use) are intended to extend to embodiments in each. Where a method of treatment is described, unless otherwise excluded, additional embodiments provide that the product composition is isolated and optionally post-treated in a manner consistent with molecular sieves or zeolite synthesis. .

The present disclosure encompasses compositions designated "CIT-13/OH," "-CIT-14," and "CIT-14/IST," and methods for converting the former to the latter.

Crystalline Microporous Germanosilicate Compositions Called CIT-14/IST and "-CIT-14"

A particular embodiment includes a crystalline microporous germanosilicate composition designated CIT-14/IST with 8- and 12-membered ring channels. These include compositions derived or derivable from CIT-13/OH through the use of concentrated strong acids.

In certain embodiments, the CIT-14/IST germanosilicate composition comprises pure germanosilicate. In other independent embodiments, the CIT-14/IST germanosilicate composition comprises one or more oxides of aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium It contains a framework. These additional oxides may come from the precursor CIT-13/OH used to prepare the CIT-14/IST germanosilicate composition. Methods of incorporating these oxides into precursor CIT-13/OH compositions are described elsewhere herein.

These crystalline microporous germanosilicate CIT-14/IST compositions have , 27.19±0.5 and 27.69±0.5 degrees 2-theta with at least 5 characteristic peaks in their powder XRD patterns. In certain independent embodiments, the powder X-ray diffraction (XRD) pattern exhibits at least 5 characteristic peaks at 5, 6, 7, 8, 9, or 10 of those characteristic peaks defined above. show. In certain independent embodiments, peak position uncertainty is independently (for each peak) ±0.5 degrees 2-theta, ±0.4 degrees 2-theta, ±0.3 degrees 2-theta, ±0.2 degrees 2-theta , ±0.15 degrees 2-theta, or ±0.15 degrees 2-theta.

Table 1 provides a list of powder XRD data from samples of the crystalline germanosilicate CIT-14/IST composition. These data are considered representative of these materials. Various permutations of these data may be used to characterize these compositions, for example, by including multiple peaks selected by their relative intensities. Additionally, these crystalline microporous germanosilicate CIT-14/IST compositions can be characterized by comparison with the powder XRD patterns shown in FIG.

[Table 2]
Table 1. Powder X-ray diffraction data for CIT-14/IST
*Observation data obtained at wavelength 0.9998A using the 2-1 powder diffraction beamline of the Stanford University Synchrotron Radiation Light Source (SSRL) for the samples shown in Tables 5 and 7 (see Experiment), Rigaku Miniflex II diffraction Peak positions (in parentheses) obtained with a 3D detector (Cu Kα line λ=1.5418 A).

For example, in another particular embodiment, the crystalline microporous germanosilicate CIT-14/IST composition is characterized by a powder X-ray diffraction (XRD) pattern exhibiting a characteristic peak of 7.59±0. . at least 3 of 5, 8.07±0.5, 19.12±0.5, 20.73±0.5, and 22.33±0.5 degrees 2-theta, and optionally 12.88±0.5, 19.32±0.5, 24.37±0.5, 27.19±0.5, and 27.69±0.5 degrees having one characteristic peak. The peaks at 7.59 and 8.07 deg2-θ, corresponding to Miller indices of (110 and (200) respectively, are the strongest peaks in the pattern. Other individual weaker peaks also help distinguish them from other materials. I think that the.

The observed intensity values in Table 1 are attributed to the completely random orientation of the crystallites, the perfect long-range order in all crystallographic directions, and the ideal connectivity of the CIT-14/IST framework. presumed to be based on However, the crystallite morphology of CIT-14/IST is very flat and exhibits a high aspect ratio, indicating that the intensity may actually be convoluted by the preferential orientation of the sample. Furthermore, the intensity of the first peak (110) (7.67) appears to increase as the crystallinity (quality) of the CIT-14 sample improves. This is because the diagonal long-range order of the connecting unit (AAA in CIT-14) contributes to (110) diffraction. The relatively chemically inert Si-rich layer is attributed to the (200) peak at 8.08°. (i.e. generally strong)

In certain embodiments, the crystalline microporous germanosilicate CIT-14/IST composition as prepared from CIT-13/OH described herein has a ratio of 12:1 to 13:1, 13:1 with Si:Ge ratios ranging from to 14. to 14:1, 14:1 to 15:1, 15:1 to 16:1, 16:1 to 17:1, 17:1 to 18:1, 18:1 to 19:1, 19:1 to 20 :1, or any combination of two or more of these aforementioned subranges, eg, 14:1 to 18:1. Certain compositions described in the examples are also considered within these ranges.

The crystals of the crystalline microporous germanosilicate CIT-14/IST are orthorhombic. As described in the examples, it may optionally be a crystal of the Cmmm space group, or a crystal of the Cmcm space group, or a disordered crystal consisting of an intracrystalline disorder of two domains.

In this context, crystals of the crystalline microporous germanosilicate CIT-14/IST composition have been found to exhibit unit cell parameters according to:

[Table 3]
The Å values in the far right column are those actually determined (or estimated) based on the Rietveld refinement (see example), while those in the middle column are for specific compositions (e.g. Si:Ge ratio , or any metal oxide substitution).

The channels within these crystalline microporous germanosilicate CIT-14/IST compositions are also characterized as follows: the 8-membered ring channels have pore dimensions of about 3.3 Å x 3.9 Å, and the 12-membered The ring channel is approximately 4. Although the respective pore sizes have been experimentally determined to be 3.26 Å x 3.93 Å and 4.86 Å x 6.44 Å, wider variations are possible, for example to accommodate physical strains (e.g., compression). Guaranteed. A wider dispersion is needed because physical strains such as compression and the Si:Ge ratio can change these values. In addition, the average metal-oxygen (TO) bond length in the framework is 1.55-1.65 Å, the average oxygen-metal-oxygen (OTO) is 98 ^o -116 ^o , and the average metal-oxygen-metal (TOT) is 139 ^o -180 ^o (T is Si or Ge).

To date, crystalline microporous germanosilicate CIT-14/IST compositions have been characterized by their physical attributes. However, the present disclosure also contemplates embodiments in which these compositions are characterized by the method of making them from the reaction of germanosilicate CIT-13/OH and concentrated strong acid. Such embodiments are those in which structure is considered independently of the physical parameters mentioned (i.e. pure product-by-product description) and those in which structure is considered simultaneously with one or more of the physical attributes. including.

In these embodiments, the crystalline microporous germanosilicate CIT-14/IST composition comprises a crystalline microporous germanosilicate designated as CIT-13/OH at an elevated temperature, asmade microporous germanosilicate". -CIT-14", prepared by contact with concentrated mineral acids for a time sufficient to form. Compositions of both CIT-13/OH (described and used herein) and "-CIT-14" are described elsewhere herein. The following description also relates to methods of preparing germanosilicate CIT-14/IST compositions from germanosilicate CIT-13/OH compositions, and of germanosilicate CIT-14/IST compositions according to these methods. It should be understood that the method of preparation constitutes an independent embodiment. This composition of CIT-13/OH germanosilicate, as well as its use in the preparation of CIT-14/IST, the composition designated "-CIT-14" is also a separate embodiment of the present disclosure. is considered.

For preparation of the CIT-14/IST composition from the germanosilicate CIT-13/OH composition, the method includes one or more of the following conditions.

(1) The CIT-13/OH composition is conveniently dispersed in an aqueous strong acid. The reaction mixture may then be static or mixed more efficiently in a moving reactor, such as a rotating reactor. As emphasized in the examples, it may be useful to physically disperse the reaction medium at intermediate times.

(2) Mineral acids are strong acids; ie, those that dissociate substantially completely in aqueous solution, as distinguished from weak acids that only partially ionize in aqueous solution. HCl and HNO( ₃ ) are representative acids, but other strong acids may be used. These strong acids are those with anions that can be incorporated into the framework lattice (eg, phosphate), but are not considered where such incorporation is considered undesirable.

(3) The use of concentrated acid appears to be important. In preferred embodiments, the mineral acid concentration ranges from 6 to 12M. Higher concentrations are preferred (eg, 10 to 12 M) as these are believed to improve reaction kinetics and yields.

(4) The elevated temperature is a temperature in the range of 80 ^° C to 120 ^° C, preferably about 95 ^° C. Considering the volatility of water at this temperature, it is necessary to use a closed reactor.

(5) Time sufficient to effect transformation ranges from 4 hours to 96 hours, preferably from 6 hours to 24 hours. Clearly, there is a balance between time, temperature, and acid type and concentration required for the reaction to proceed to an adequate yield of product. Conditions corresponding to 95 ^° C. for 6 hours using 12M aqueous HCL have been found to be suitable.

(6) Following contact of the germanosilicate with an acid, the resulting demanganized germanosilicate is isolated under the designation "-CIT-14". This is conveniently done by centrifugation, although these other separation methods may be used.

(7) The isolated "-CIT-14" material is then rinsed or washed repeatedly with water (preferably distilled or deionized water) until the wash is pH neutral. This "-CIT-14" material is also considered a separate embodiment of this disclosure, and representative features of this material are described in the Examples.

(8) heat this isolated and washed "-CIT-14" material at a temperature ranging from about 450 ^° C to 650 ^° C for a time ranging from 2 hours to 12 hours, preferably 580 ^° C for 6 hours; CIT-14/IST can be prepared from this off-the-shelf "-CIT-14" material by heating for hours, or substantially equivalent conditions. In a preferred embodiment, heating is performed at a temperature ramp rate of 1-5 ^° C./min, preferably 1 ^° C./min.

Conversion of CIT-13/OH to CIT-14/IST is accompanied by a decrease in micropore volume on the order of 25-30 vol%.

The foregoing method is consistent with the mechanism characterized as the inverse sigma transformation of crystalline microporous CIT-13/OH germanosilicates for the reasons given in the discussion section of the Examples, CIT-14/IST germanosilicates I will provide a. As such, the methods and products may be characterized using that term.

Crystalline microporous germanosilicate composition, name: CIT-13/OH

Compositions generally defined as CIT-13 and their reactivity under various processing conditions have been previously reported. See, for example, U.S. Pat. Nos. 10,293,330 and 10,828,625 and U.S. Patent Application Publication No.-0252729, each of which for all purposes, or at least the germanosilicate CIT-13. shall be incorporated herein by reference with respect to information relating to

U.S. Pat. No. 10,293,330 states that CIT-13 has a three-dimensional framework with pore channels defined by 10- and 14-membered rings and has a powder XRD pattern as shown in Table 2. is described as indicating

[Table 4]
Table 2. Powder XRD peaks of CIT-13. Estimated variability of 2-θ is ±0.2 ^o . The actual intensity often differs from the theoretical value. U.S. Patent No. 10,293,330.

The CIT-13/OH germanosilicates described herein also have a three-dimensional framework with pores defined by 10- and 14-membered rings, but are fluoride-free. Consistent with other CIT-13 germanosilicates, they exhibit at least five peaks at 6.45±0.2, 7.18±0.2, 12.85±0.2, 20.78±0.2, 26.01±0.2, and 26.68±0.2 degrees 2-θ. 1 shows a powder XRD (X-ray diffraction) pattern with See Table 2. These CIT-13/OH germanosilicates are characterized by a powder XRD pattern with peaks at 6.45±0.2 and 7.18±0.2 degrees 2-theta, and 5, 6 or 7 of the other peaks shown in Table 2. sometimes attached.

As discussed in the Examples, the powder XRD patterns of CIT-13/OH described herein show some differences from the data presented in Table 2, particularly with respect to the intensity of the (200) peak of the asmade material. showing. This observation is further elaborated in the examples. In some embodiments, the peak at 6.45±0.2 degrees 2-theta is reduced in intensity (weaker) relative to the peak at 7.18±0.2 degrees 2-theta, with the latter peak being the strongest in the pattern (Example checking). In another embodiment, the powder XRD pattern of CIT-13/OH germanosilicate exhibits an additional peak at 11.58 degrees ±0.2 degrees 2-theta of moderate to weak intensity attributed to the (310) index.

The CIT-13/OH germanosilicate also exhibits a ²⁹ SiMAS-nmr spectrum consistent with that shown in Figure 12 (top). This is explained further in the examples.

The Si:Ge ratios of these CIT-13/OH germanosilicates range from 3.5 to 3.6, 3.6 to 3.7, 3.7 to 3.8, 3.8 to 3.9, 3.9 to 4.0, 4.0 to 4.1, 4.1 to 4.2, 4.2 to 4.3, 4.3. to 4.4, 4 to 4.4 to 4.5, 4.5 to 4.6, 4.6 to 4.7, 4.7 to 4.8, 4.8 to 4.9, 4.9 to 5.0, 5.0 to 5.2, or any two or more of the foregoing ranges Defined to be in the range, eg 3.5 to 5.2 or 3.5 to 3.9. These ranges are similar to those reported previously for the CIT-13 material.

However, unlike those previously reported materials, the instant fluoride-free CIT-13/OH germanosilicate has an average of at least 4 and preferably more than 4 Ge atoms per d4r unit. It contains a d4r structural unit, allowing the presence of Ge-4-rings in the d4r unit. This feature allows these materials to unexpectedly transform into the corresponding CIT-5 and "-CIT-14"/CIT-14/IST materials. Again, these features are further illustrated in the Examples.

One such method for determining the average number of Ge atoms in the d4r units is the addition of fluoride ions to CIT-13/OH germanosilicate and ¹⁹ FMAS-nmr analysis of the resulting doped material. This includes spectral measurements and is described in the Examples.

Critical to the final structure of the CIT-13/OH materials is the manner in which they are made in the complete absence of fluoride ions. As described herein, the crystalline microporous germanosilicate CIT-13/OH composition is prepared by a method comprising hydrothermally treating an aqueous composition obtained from the admixture.
(a) It is a source of silicon oxide ( _SiO2 ).
(b) a source of germanium oxide ( _GeO2 ); and
(c) be any source of aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combinations or mixtures thereof;
(d) at least one hydroxide salt of a substituted benzylimidazolium organic structure director (OSDA) cation having the structure:

[Chemical 1]
(e) optionally, at least one compositionally matched seed crystal; and
(f) water. under conditions effective to crystallize a crystalline microporous germanosilicate composition designated CIT-13/OH;
(a) Si:Ge molar ratio in the range of 2 to 4, preferably 2.
(b) Water with a water:Si molar ratio in the range of 8:1 to 12:1.
(c) water having a molar ratio of water:(SiO ₂ +GeO ₂ ) in the range of 6:1 to 7:1;
(c) containing hydroxide ions (OH) in a molar ratio of OH:(SiO ₂ +GeO ₂ ) in the range of about 0.3:1 to 0.7:1;
where the aqueous composition is essentially free of fluoride ions.

These ranges are tighter than previously reported. This range is important for producing Ge-rich d4r units.

Within this framework, the method includes one or more of the following features.

(1) The source of silicon oxide can be any source known to be suitable for molecular sieve synthesis, but in preferred embodiments silicic acid, silica hydrogel, silicic acid, fumed silica, colloidal silica , tetraalkylorthosilicate, silica hydroxide, or combinations (or equivalent sources) thereof, preferably sodium silicate or tetraalkylorthosilicate, more preferably tetraethylorthosilicate (TEOS).

(2) The source of germanium oxide can be any source known to be suitable for molecular sieve synthesis, the source of germanium oxide being _GeO2 , or its hydrated derivatives (or equivalent). source).

(3) Substituted benzylimidazolium organic structure directing agent (OSDA) cations have an OSDA:( _SiO2 + _GeO2 ) molar ratio in the range of about 0.3:1 to 0.7:1, preferably about 0.4:1 to 0.6:1. exists in

(4) The aqueous composition is essentially free of alkali metal cations, alkaline earth metal cations or diones, or combinations thereof.

(5) The at least one substituted benzylimidazolium organic structure director (OSDA) cation preferably has a structure.

[Chemical 2]

(6) Aqueous compositions are suspensions or gels.

(7) Effective crystallization conditions include subjecting the mixture to a temperature of about 140 ^° C. to about 180 ^° C. and a time of about 4 days to about 4 weeks.

(7) hydrothermally treating the aqueous composition in a rotary oven;

(8) The method further comprising isolating the crystalline microporous germanosilicate solid composition.

The CIT-14/IST described herein is compositionally distinct from the CIT-14/ESP (ESP means ethoxysilylated pillar) structure previously reported in US Patent Application Publication. . 2017/0252729, which is incorporated herein by reference for all purposes or at least for these disclosures. These previously reported CIT-14/ESPs catalyzed phyllosilica of CIT-13P topology at about 165 ^° C. to about 225 ^° C. in the presence of a concentrated mineral acid (e.g., HCl, or preferably HNO ₃ ). to form an intermediate composition for a time ranging from 12 to 48 hours at one or more temperatures ranging from It is prepared by forming a composition.

In particular, CIT-14/ESP germanosilicates were formed using CIT-13P phyllosilicates, which have much higher Si:Ge ratios than described by extemporaneous methods, with Si:Ge ratios ranging from about 25 to substantially obtained CIT-14/ESP germanosilicates to infinity, including embodiments in which Si:Ge was from about 25 to about 150, or from about 75 to about 150. The quality of crystals formed by the ADOR process was lower than reported here.

These CIT-14/ESP germanosilicates exhibited powder X-ray diffraction (XRD) patterns not significantly different from those reported for the CIT-14/IST germanosilicates: 7.7, 8.2, 13.1, 19.5, 21.1, It is reported that there are at least five characteristic peaks at 22.7 and 27.6 degrees 2-theta. Due to structural disturbances in the material, the observed diffraction peaks are broad and the error assigned to these peaks is ±0.5 degrees 2-theta. In other embodiments, the error associated with these peaks is ±0.3. It was degree 2-θ. Consistent with other structures made by pillar rings, and how they can be made, the structure of this new material is a three-dimensional framework with pores defined by 8- and 12-membered rings. described from the point of view. From the theoretical structure, the dimensions of the 8- and 12-membered rings were calculated to be 4.0x3.4 Å and 6.9x5.4 Å, respectively (see Figures 3(A)-(B)). 3(A-B)). The PXRD patterns identified from the isolated products are not identical, but are consistent with the theoretical value associated with this structure (predicted by the General Utility Lattice Program, GULP (Gale, 1997)), namely silica-rich It is to have silica pillars separating the CFI layers. Such pattern differences were thought to be explained by structural disorder and imperfect columnarization of silica. In this case, the version of CIT-14/ESP can also be described in terms of the crystallographic parameters shown in FIGS. 3(A) and 3(B). It can also be explained by the crystallographic parameters shown in 3(A) and 3(B).

[Table 5]
Table 3. Comparison of theoretical and measured PXRD patterns of CIT-14/ESP generated by ADOR transformation. Data are described in US Patent Application Publication No. 2017/0252729.

Other Variations in Microcrystalline Compositions In certain embodiments, the crystalline microcrystalline compositions described in the present disclosure comprising CIT-13/OH germanosilicate and the newly described microcrystalline CIT-14/IST germanosilicate. Porous solids exist in their hydrogen form. In other embodiments, the crystalline microporous solid contains at least one metal cation salt or transition metal or salt within its micropores. In other specific embodiments, the metal cation salts are K ⁺ , Li ⁺ , Rb ⁺ , Ca ²⁺ , Cs ⁺ : Co ²⁺ , Cu ²⁺ , Mg ²⁺ , Sr ²⁺ , Ba ²⁺ , Ni ²⁺ , or Fe ²⁺ , copper salts are, for example, Schweiser's reagent (tetraamminediaqua copper dihydroxide, [Cu(NH ₃ ) ₄ (H ₂ O) ₂ ](OH) ₂ ]), copper nitrate (II ) or copper (II) carbonate. Such metal cations can be incorporated, for example, using techniques known to be suitable for this purpose (eg, ion exchange).

In other embodiments, the pores may contain transition metals or transition metal oxides. Addition of such materials may be accomplished by, for example, chemical vapor deposition or chemical precipitation. In an independent embodiment, the transition metal or transition metal oxide comprises a Group 6, 7, 8, 9, 10, 11, or 12 element. In other independent embodiments, the transition metal or transition metal oxide is scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium , platinum, copper, silver, gold, or mixtures. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred. In independent embodiments, the aqueous ammonium salts or metal salts or chemically deposited or precipitated materials are independently Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Be, Al, Ga , In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, or R _4-n N ⁺ H _n cation, R is alkyl , n=0-4 in at least some of its pores.

Although the term "transition metal" is defined elsewhere herein, in certain other independent embodiments the transition metal or transition metal oxide is selected from Groups 6, 7, 8, 9 Group 10, Group 11, or Group 12 elements. In yet another independent embodiment, the transition metal or transition metal oxide is scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, Consists of palladium, platinum, copper, silver, gold, or mixtures. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred dopants.

In other embodiments, the optionally doped crystalline solid is 400° C. to 500 ^{° C.} , 500 ^° C. to 600° C., 600 ^° C. to 700 ^° C., ^{700° C.} to 800 ^° C., 800 ^° C. calcined in air at a temperature defined as being in at least one of the ranges C to 900 ^° C, 900 ^° C to 1000 ^° C, 1000 ^° C to 1200 ^° C, 500 ^° C to about 1000 ^° C . The choice of a particular temperature may in some cases be limited by the stability (decomposition or conversion to another crystalline phase) of the particular solid.

Other methods for modifying molecular sieves for use as catalysts are known to those skilled in the art, and such additional modifications are considered within the scope of this disclosure.

Uses of the Compositions of the Invention - Catalytic Conversion/Separation In various embodiments, the crystalline microporous germanosilicate solids as disclosed herein are calcined, doped, or treated as described herein. and act as catalysts to mediate or catalyze sequences of chemical transformations or separations. All such combinations of compositions and catalysis are considered individual embodiments of the present disclosure as if they were individually and separately defined. The use of these germanosilicates for these purposes is also within the scope of this disclosure. Such transformations/separations include carbonylation of DME (dimethyl ether) with CO at low temperatures, reduction of NOx with methane (e.g. for exhaust applications), cracking, hydrocracking, dehydrogenation, paraffin to aroma delipidation of hydrocarbon feedstocks, MTO (methanol to olefins), isomerization of aromatics (e.g. xylenes), disproportionation of aromatics (e.g. alkylation of aromatics, Oligomerization, amination of lower alcohols, separation and sorption of lower alkanes, hydrocracking of hydrocarbons, degreasing of hydrocarbon feedstocks, isomerization of olefins, production of high molecular weight hydrocarbons from low molecular weight hydrocarbons, production of high molecular weight hydrocarbons from low molecular weight hydrocarbons, Converting reformers, lower alcohols or other oxygenated hydrocarbons to olefin products Epoxidizing olefins with hydrogen peroxide, reducing the content of oxides of nitrogen in gas streams in the presence of oxygen or separating nitrogen from a nitrogen-containing gas mixture, wherein the respective source is subjected to crystalline microencapsulation of any one of the materials described herein under conditions sufficient to affect the named transformation. Particularly attractive applications include catalytic cracking, hydrocracking, degreasing, alkylation, and olefin and aromatics where these germanosilicates are expected to be useful. group formation reactions, etc. It is also used for gas drying and separation.

Certain embodiments provide hydrocracking processes, each process contacting a hydrocarbon feedstock under hydrocracking conditions with a catalyst composed of the crystalline microporous solids of the present disclosure (preferably predominantly in hydrogen form). Including.

Yet other embodiments provide processes for degreasing a hydrocarbon feed, each process comprising contacting the hydrocarbon feed under degreasing conditions with a catalyst comprising the crystalline microporous solids of the present disclosure. Yet other embodiments provide processes for improving the viscosity index of a dewaxed product of a waxy hydrocarbon feed, each process comprising converting a waxy hydrocarbon feed under isomerization dewaxing conditions to the crystalline microparticles of the present disclosure. Including contacting with a catalyst comprising a porous solid.

Additional embodiments include those processes for producing C20+ lubricants from C20+ olefin feeds, each process comprising isomerization over a catalyst comprising at least one transition metal catalyst and the crystalline microporous solids of the present disclosure. isomerizing said olefin feed under conditions.

The present disclosure also includes processes for isomerizing and degreasing a raffinate, each process comprising, in the presence of added hydrogen, converting said raffinate, such as bright stock, to at least one transition metal and It includes contacting with a catalyst comprising a crystalline microporous solid.

Another embodiment is a hydrocarbon oil feed boiling above about 350 ^° F. and containing straight and slightly branched chain hydrocarbons in the presence of added hydrogen gas at a hydrogen pressure of about 15 to psi. provides dewaxing comprising contacting at least one transition metal and a catalyst comprising a crystalline microporous solid of the present disclosure, preferably in predominantly hydrogen form.

The present disclosure also includes hydrocracking a hydrocarbonaceous feedstock in a hydrocracking zone to obtain an effluent comprising hydrocracking oil and containing at least one transition metal and the crystalline microporous solids of the present disclosure. catalytically dewaxing said effluent comprising hydrocracking oil in the presence of added hydrogen gas at a temperature of at least about 400 ^° F. and a pressure of about 15 psig to about 3000 psig. process is included.

The present disclosure also includes processes for octane enrichment of a hydrocarbon feedstock to produce products with increased aromatic content, each process comprising a contacting a hydrocarbonaceous feedstock consisting of conventional hydrocarbons and slightly branched hydrocarbons having a boiling range of less than be done. In these embodiments, the crystalline microporous solid is preferably rendered substantially acid free by neutralizing the solid with a basic metal. Also provided in this disclosure is such a process wherein the crystalline microporous solid comprises a transition metal component.

Also provided by the present disclosure are catalytic cracking processes, each process comprising a hydrocarbon feedstock in a reaction zone under catalytic cracking conditions in the absence of added hydrogen to produce the crystalline microporous solids of the present disclosure. contacting with a catalyst comprising; The present disclosure also includes such catalytic cracking processes in which the catalyst further comprises a large pore crystalline cracking component.

The present disclosure further provides isomerization processes for isomerizing C4-C7 hydrocarbons, each process producing a feed having normal and slightly branched C4-C hydrocarbons under isomerization conditions, preferably comprising contacting a catalyst consisting of a crystalline microporous solid of the present disclosure primarily in the hydrogen form. The crystalline microporous solid may be impregnated with at least one transition metal, preferably platinum. The catalyst may be calcined at elevated temperature in a steam/air mixture after transition metal impregnation.

Also provided by the present disclosure are processes for alkylating aromatic hydrocarbons, each process comprising, under alkylating conditions, at least a molar excess of an aromatic hydrocarbon and a C2-C20 olefin to at least a partial liquid contacting in the presence of a catalyst consisting of a crystalline microporous solid of the present disclosure (preferably predominantly in the hydrogen form) under phase conditions. The olefin may be a C2-C4 olefin and the aromatic hydrocarbon and olefin may be present in a molar ratio of about 4:1 to about 20:1 respectively. Aromatic hydrocarbons may be selected from the group consisting of benzene, toluene, ethylbenzene, xylenes, or mixtures thereof.

Further provided in accordance with the present disclosure are processes for transalkylating aromatic hydrocarbons, each of the processes comprising under transalkylation conditions, at least partial liquid phase conditions, a crystal of the present disclosure. It comprises contacting an aromatic hydrocarbon, preferably predominantly in the hydrogen form, with a polyalkylaromatic hydrocarbon in the presence of a catalyst consisting of a ionic microporous solid. The aromatic hydrocarbon and polyalkylaromatic hydrocarbon may be present in molar ratios of about 1:1 to about 25:1, respectively. The aromatic hydrocarbon may be selected from the group consisting of benzene, toluene, ethylbenzene, xylene, or mixtures thereof, and the polyalkylaromatic hydrocarbon may be dialkylbenzene.

Further provided by the present disclosure are processes for converting paraffins to aromatics, each of the processes comprising a catalyst comprising the crystalline microporous solids of the present disclosure under conditions conducive to converting paraffins to aromatics. The catalyst comprises gallium, zinc, or a compound of gallium or zinc.

Also provided in accordance with the present disclosure is a process for isomerizing an olefin, each process comprising contacting the olefin with a catalyst comprising the crystalline microporous solids of the present disclosure under conditions that cause isomerization of the olefin. .

Further provided in accordance with the present disclosure are processes for isomerizing an isomerization feed, each process comprising an aromatic C8 stream of xylene isomers or a mixture of xylene isomers and ethylbenzene, wherein ortho, meta and A more nearly equilibrium ratio of para-xylene is obtained and the process comprises contacting the feed with a catalyst comprising the crystalline microporous solids of the present disclosure under isomerizing conditions.

The present disclosure further provides processes for oligomerizing olefins, each process comprising contacting an olefin feed with a catalyst comprising the crystalline microporous solids of the present disclosure under oligomerization conditions.

The present disclosure also provides processes for converting lower alcohols and other oxygenated hydrocarbons, each process comprising the conversion of said lower alcohol (e.g., methanol, ethanol or propanol) or other oxygenated hydrocarbons under conditions that produce a liquid product. comprising contacting an oxygenated hydrocarbon with a catalyst comprising the crystalline microporous solids of the present disclosure.

Also provided by the present disclosure are processes for reducing oxides of nitrogen contained in a gas stream in the presence of oxygen, each process converting the gas stream to the crystalline microporous solid of the present disclosure. includes contacting with The crystalline microporous solid may contain metals or metal ions (such as cobalt, copper, or mixtures thereof) that can catalyze the reduction of oxides of nitrogen, in the presence of a stoichiometric excess of oxygen. may be implemented. In a preferred embodiment, the gas stream is the exhaust stream of an internal combustion engine.

Hydrogen and carbon monoxide, also referred to as synthesis gas or synthesis gas, using catalysts composed of any of the germanosilicates described herein, including those with the CIT-13 framework, and Fischer-Tropsch catalysts. Also provided is a process for converting a syngas containing to a liquid hydrocarbon fuel. Such catalysts are described in US Pat. No. 9,278,344, which is incorporated by reference for its teachings and methods of using catalysts. The Fischer-Tropsch component comprises a group 8-10 transition metal component (ie Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), preferably cobalt, iron and/or ruthenium. The optimum amount of catalytically active metal present depends, inter alia, on the particular catalytically active metal. Typically, the amount of cobalt present in the catalyst may range from 1 to 100 parts by weight per 100 parts by weight of support material, preferably from 10 to 50 parts by weight per 100 parts by weight of support material. In one embodiment, 15 to 45 wt% cobalt is deposited on the hybrid support as the Fischer-Tropsch component. In another embodiment, 20 to 45 wt% cobalt is deposited on the hybrid support. The catalytically active Fischer-Tropsch component may be present in the catalyst together with one or more metal promoters or cocatalysts. Promoters can be present as metals or as metal oxides, depending on the particular promoter involved. Preferred promoters are metals or oxides of transition metals, including lanthanides and/or actinides, or oxides of lanthanides and/or actinides. Alternatively, or in addition to metal oxide promoters, the catalyst may comprise a metal promoter selected from Group 7 (Mn, Tc, Re) and/or Groups 8-10. In some embodiments, the Fischer-Tropsch component further comprises a cobalt reduction accelerator selected from the group consisting of platinum, ruthenium, rhenium, silver, and combinations thereof. The method employed to deposit the Fischer-Tropsch component on the hybrid support requires the use of a soluble cobalt salt to achieve the metal loading and distribution required to provide a highly selective and active hybrid syngas conversion catalyst. and optionally impregnation techniques using aqueous or non-aqueous solutions containing soluble promoter metal salts such as platinum salts.

Still further process embodiments include those for reducing the halogen compound concentration in the initial hydrocarbon product containing undesirable levels of organohalogen compounds, wherein the process reduces at least a portion of the hydrocarbon product to , under organohalogen compound absorption conditions, to reduce the halogen concentration in the hydrocarbon by contacting it with a composition comprising any of the germanosilicate structures described herein, including CIT-13. Initial hydrocarbon products may be produced by a hydrocarbon conversion process using an ionic liquid catalyst comprising a halogen-containing acidic ionic liquid. In some embodiments, the organic halide content in the initial hydrocarbon product ranges from 50 to 4000 ppm, and in other embodiments the halogen concentration is reduced. In other embodiments, production may achieve reductions of 85%, 90%, 95%, 97%, or more. The initial hydrocarbon stream may consist of alkylates or gasoline alkylates. Preferably, the hydrocarbon alkylate or alkylate gasoline product is not cracked during contacting. Any of the materials or process conditions described in US Pat. No. 8,105,481 are believed to describe the range of materials and process conditions of the present disclosure. US Pat. No. 8,105,481 is incorporated by reference for at least its teachings regarding methods and materials used to effect such transformations (both alkylation and halogen reduction).

A still further process embodiment comprises contacting a hydrocarbonaceous feedstock consisting of normal and slightly branched hydrocarbons having a boiling range of greater than about 40° C. and less than about 200° C. with a catalyst under aromatics conversion conditions. to increase the octane of a hydrocarbonaceous feedstock to produce a product with increased aromatic content.

Specific conditions for many of these transformations are known to those skilled in the art. Exemplary conditions for such reactions/transformations are described in WO/1999/008961, U.S. Pat. Nos. 4,544,538, 7,083,714, 6,841,063, 6,827,843, each It may be incorporated herein by reference in its entirety for at least these purposes.

Depending on the type of reaction catalyzed, the microporous solid may be predominantly in the hydrogen form, partially acidic, or have substantially no acidity. Those skilled in the art will be able to define these conditions without undue effort. As used herein, "predominantly in the hydrogen form" means that after calcination (which may also include exchange with _NH4 ⁺ prior to calcination), at least 80% of the cationic sites is occupied by hydrogen ions and/or rare earth ions.

The germanosilicates of the present disclosure can also be used as adsorbents for gas separation. For example, such germanosilicates may be used as hydrocarbon traps, eg, cold start hydrocarbon traps in combustion engine pollution control systems. In particular, such germanosilicates are believed to be particularly useful for trapping _C3 fragments. Such embodiments may include a process and apparatus for trapping low molecular weight hydrocarbons from an incoming gas stream, the process having a reduced concentration of low molecular weight hydrocarbons compared to the incoming gas stream. passing or passing a gas stream through a composition comprising any one of the crystalline microporous germanosilicate compositions described herein to provide an exiting gas stream having a In this context, the term "low molecular weight hydrocarbons" refers to C1-C6 hydrocarbons or hydrocarbon fragments.

The germanosilicates of the present disclosure may also be used in processes for treating cold-start engine exhaust gas streams containing hydrocarbons and other pollutants, which process reduces the engine exhaust gas stream to carbonization rather than water. providing a first exhaust stream over one of the germanosilicate compositions of the present disclosure that preferentially adsorb hydrogen. flowing a first exhaust gas stream over a catalyst for converting residual hydrocarbons and other pollutants contained in the first exhaust gas stream to harmless products to provide a treated exhaust stream; to the atmosphere.

The germanosilicates of the present disclosure can also be used to separate gases. For example, they can be used to separate water, carbon dioxide, and sulfur dioxide from fluid streams such as low grade natural gas streams. Typically, molecular sieves are used as components of membranes used to separate gases. Examples of such membranes are disclosed in US Pat. Nos. 6,508,801 and 6,508,860.

For each of the foregoing processes described, additional corresponding embodiments include those comprising apparatus or systems that include or include the materials described for each process. For example, in gas trap gases, additional embodiments include those devices known in the art as hydrocarbon traps that can be placed in the exhaust gas path of a vehicle. In such devices, hydrocarbons are adsorbed in a trap and stored until the engine and exhaust reach temperatures sufficient for desorption. The device may also include a membrane comprising a germanosilicate composition useful in the described processes.
Glossary

In this disclosure, the singular forms "a," "an," and "the" include plural references, and reference to a particular numerical value includes at least that particular numerical value unless the context clearly dictates otherwise. Contains numeric values. Thus, for example, reference to "a material" is a reference to at least one such material and/or equivalents thereof known to those skilled in the art, and so on.

When values are expressed as approximations by use of the descriptor "about," it will be understood that the particular value forms another embodiment. In general, use of the term "about" indicates an approximation that may vary depending on the desired properties sought to be obtained by the disclosed subject matter and is to be interpreted in the particular context in which it is used, based on its function. It is a thing. A person skilled in the art will be able to make a routine interpretation. In some cases, the number of significant digits used for a particular value can be one non-limiting way of determining the scope of the term "about." In other cases, the gradation used in the series of values can be used to determine the intended range available for the term "about" for each value. Where present, all ranges are inclusive and combinable. That is, reference to values stated in ranges include every value within that range.

It will be appreciated that certain features of the disclosure that are, for clarity, described in this specification in the context of separate embodiments can also be provided in combination in a single embodiment. That is, each individual embodiment is considered combinable with any other embodiment(s), and such combination is not possible with another embodiment, unless expressly incompatible or expressly excluded. considered to be. Conversely, various features of the disclosure that are, for brevity, described in the context of a single embodiment may also be provided separately or in any subcombination. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each said step is also an independent embodiment in its own right, and other It can be considered that it can be combined with

The transitional terms "comprising," "consisting essentially of," and "consisting" are intended to mean their generally accepted meanings in patent terminology; namely: (i) "including"; "Comprising" synonymous with "including" or "characterized by" is inclusive or open and does not exclude additional, unmentioned elements or method steps. (ii) “consisting of” excludes any element, step, or ingredient not specified in the claim; (iii) "consisting essentially of" defines the scope of the claim as specified materials or steps that "do not materially affect the basic and novel character(s)" of the claimed disclosure; Limited to Embodiments described in terms of the phrase "comprising" (or equivalents thereof) also serve as embodiments independently described in terms of "consisting of" and "consisting essentially of." For those embodiments provided in terms of "consisting essentially of The easy operability of the object/system or the ability of the system to use only the listed ingredients.

The term "meaningful product yield" is intended to reflect product yields as described herein, including those greater than 20%, but where specified: The term can also refer to yields of 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or 90% or more relative to the amount of original substrate.

When a list is presented, each individual element of the list and all combinations of the list are understood to be separate embodiments unless otherwise specified. For example, a list of embodiments presented as "A, B, or C" may be listed as separate embodiments with "A," "B," "C," "A or B," "A or C," It should be construed to include "B or C" or "A, B, or C" embodiments.

Throughout this specification, terms should be given their ordinary meaning as understood by those of ordinary skill in the relevant arts. However, for the avoidance of doubt, the meaning of certain terms is specifically defined or clarified.

The term "alkyl" as used herein, although not necessarily containing 1 to about 6 carbon atoms, typically refers to straight chain, branched or cyclic saturated hydrocarbon groups, such as Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like.

"Aromatic" refers to cyclic moieties that satisfy the Hückel 4n+2 rule for aromaticity, and includes both aryl (ie, carbocyclic) and heteroaryl structures.

The term "halide" is used in its conventional sense to mean chloride, bromide, fluoride, or iodide.

"Lower alcohol" or lower alkane means an alcohol or alkane having 1 to 10 carbon atoms, linear or branched, preferably 1 to 6 carbon atoms, preferably linear, respectively. Methanol, ethanol, propanol, butanol, pentanol, hexanol are examples of lower alcohols. Examples of lower alkanes include methane, ethane, propane, butane, pentane, hexane.

As used herein, unless otherwise specified, the term "elevated temperature" typically refers to at least one temperature within the range of about 170 ^° C to about 230 ^° C. The term calcination is reserved for higher temperatures. Unless otherwise specified, it refers to one or more temperatures ranging from about 450 ^° C to about 800 ^° C.

As used herein, the term "metal or metalloid" as in "metal or metalloid source" or "metal or metalloid oxide" refers to those groups 4, 5, 8 of the periodic table. Refers to the elements of Groups 1, 13, 14, and 15. These elements are typically included as oxides in molecular sieves and include, for example, aluminum, boron, gallium, hafnium, iron, silicon, tin, titanium, vanadium, zinc, zirconium, or combinations thereof.

Typical sources of silicon oxide for the reaction mixture include alkoxides, hydroxides, or oxides of silicon, or combinations thereof. Exemplary compounds also include silicates (including sodium silicate), silica hydrogels, silicic acid, fumed silica, colloidal silica, tetraalkylorthosilicates, silica hydroxides, or combinations thereof. Sodium silicates or tetraorthosilicates such as tetraethylorthosilicate (TEOS), diethoxydimethylsilane (DEDMS) and/or 1,3-diethoxy-1,1,3,3-tetramethyldisiloxane (DETMDS) are preferred supplies. is the source.

Sources of germanium oxide include alkali metal orthogermanates, M ₄ GeO ₄ , GeO(OH) ₃ ⁻ containing discrete GeO ₄ ^4- ions, GeO ₂ (OH) ₂ ^2- , [(Ge(OH ) ₄ ) ₈ (OH) ₃ ] ^3- or neutral solutions of germanium dioxide can contain Ge(OH) ₄ or their alkoxide or carboxylic acid derivatives.

Typical sources of aluminum oxide for the reaction mixture include aluminates, alumina, aluminum colloids, aluminum alkoxides, aluminum oxide coated on silica sol, hydrated alumina gels such as Al(OH) ₃ , and sodium aluminate. is included. The source of aluminum oxide may also consist of an alkoxide, hydroxide, or oxide of aluminum, or a combination thereof. Additionally, the source of alumina may also contain other ligands as well, such as acetylacetonate, carboxylates, and oxalates; such compounds are useful in hydrothermal or sol-gel synthesis. well known as. Other sources of aluminum oxide can include aluminum salts such as _AlCl3 , Al(OH) ₃ , Al( _NO3 ) ₃ , and _Al2 ( _SO4 ).

Sources of boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, and/or zirconium oxide can be added in forms corresponding to their aluminum and silicon counterparts. It is possible.

As used herein, the term "mineral acid" refers to mineral acids conventionally used in molecular _sieve zeolite synthesis, such as HCl, HBr, HF, _HNO3 , or _H2SO4 . Also, oxalic acid or other strong organic acids can be used instead of mineral acids. Generally, HCl and _HNO3 are the preferred mineral acids. As used throughout this specification, the terms "concentrated" and "diluted" with respect to mineral acids mean concentrations greater than 0.5 M and concentrations less than 0.5 M, respectively. In some embodiments, the term "enriched" means one or more concentrations in the range 0.5 to 0.6, 0.6 to 0.7, 0.7 to 0.8, 0.8 to 0.9, 0.9 to 1, 0.0, 1.0 to 1.1, 1.1 to 1.2, 1.2 to 1.3, 1.3 to 1.4, 1.4 to 1.5, 1.5 to 1.6, 1.6 to 1.7, 1.7 to 1.8, 1.8 to 1.9, 1.9 to 2.0 or higher. Similarly, the term "dilution" means one or more concentrations in the ranges 0.5 to 0.4, 0.4 to 0.3, 0.3 to 0.2, 0.2 to 0.15, 0.15 to 0.1, and 0.1 to 0.05. In the experiments and preferred embodiments described herein, dilute acids refer to those in the composition range of 0.5 to 0.15M.

The term "CIT-13" topology describes a crystalline microporous composition similar to that described in US Pat. No. 10,293,330 with a set of orthogonally oriented 14-membered pores. The term "phyllosilicate" refers to a two-dimensional layered structure of silica-containing oxides, as described in US Patent Application Publication No. 2017/0252729.

The terms "oxygenated hydrocarbon" or "oxygenating agent" as known in the hydrocarbon processing arts are those known to be present in hydrocarbon streams or biomass streams or other sources (e.g. known to refer to ingredients containing alcohols, aldehydes, carboxylic acids, ethers, and/or ketones obtained from fermented sugar (ethanol).

The terms "separate" or "separated" refer to the physical separation or separation of a solid product material from by-products or by-products (impurities) associated with reaction conditions that yield other starting materials or materials. Where it is meant, it has its ordinary meaning as will be understood by those skilled in the art. As such, one skilled in the art would at least be cognizant of the presence of the product and would reason to take specific actions to separate or segregate it from the starting materials and/or by-products. Absolute purity is not required, but is preferred. When the term is used in the context of gas processing, the term "separation" or "separation", as understood by those skilled in the art, refers to the division of gases by adsorption or by osmosis based on size or physical or chemical properties. means.

Unless otherwise indicated, the term "isolated" means physically separated from other components so as to be free of at least solvent or other impurities such as starting materials, by-products, or by-products. . In some embodiments, isolated crystalline materials are considered isolated if, for example, they are separated from the reaction mixture that gave rise to their preparation, from mixed-phase co-products, or both. be able to. In some of these embodiments, pure germanosilicates (including structures with or without incorporated OSDA) can be produced directly from the methods described. In some cases, crystalline phases may not be separated from each other, in which case the term "isolated" may refer to their separation from their source composition.

According to the IUPAC notation, the term "microporous" means materials with pore sizes of less than 2 nm. Similarly, the term "macroporous" refers to materials with pore sizes greater than 50 nm. And the term "mesoporous" refers to materials whose pore sizes are intermediate between microporous and macroporous. In the context of the present disclosure, material properties and applications depend on scaffold properties such as pore size and dimensions, cage dimensions and material composition. As such, there is often only a single framework and composition that provides optimal performance in a desired application.

"Optional" or "optionally" means that the subsequently described situation may or may not occur, and thus the description includes examples in which the situation occurs and in which it does not. . For example, the phrase "optionally substituted" indicates that non-hydrogen substituents may or may not be present on a given atom, thus structures with non-hydrogen substituents present and structures without non-hydrogen substituents. means a description that includes

The terms "method(s)" and "process(es)" are considered interchangeable within this disclosure.

As used herein, the term "crystalline microporous solid" or "crystalline microporous germanosilicate" refers to a crystalline structure having a very regular pore structure of molecular dimensions, i.e., 2 nm or less. be. The maximum size of species that can enter the pores of a crystalline microporous solid is controlled by the channel dimensions. These terms may also refer specifically to CIT-13 compositions.

As used herein, the term “pillaring” generally refers to the process of introducing stable metal oxide structures (“so-called “pillars”) between substantially parallel crystalline silicate layers. The metal oxide structure maintains separation of the silicate layers and is created by spacings between the layers of molecular dimensions. The term is generally used in the context of clay chemistry and is well understood by those skilled in the art of clays and zeolites, particularly when applied to catalysis.

The term "germanosilicate" means any composition containing oxides of silicon and germanium in its framework. The term "pure" "pure germanosilicate" means that these compositions contain only germania and silica, respectively, as far as practicable, and other metal oxides in the framework are inevitable and unintended. , means that it is present as an impurity. The germanosilicate may be "pure germanosilicate" or optionally substituted with other metal oxides or metalloid oxides. Similarly, the terms aluminosilicate, borosilicate, ferrosilicate, stannosilicate, titanosilicate, or zincosilicate structures include silicon oxides and oxides of aluminum, boron, iron, tin, titanium, and zinc, respectively. It is a thing. When referred to as "optionally substituted", each skeleton includes aluminum, boron, gallium, germanium, hafnium, iron, tin, substituted with one or more atoms or oxides not already present in the parent skeleton. It may contain titanium, indium, vanadium, zinc, zirconium, or other atoms or oxides.

As used herein, the term "transition metal" refers to any element in the d block of the periodic table, including groups 3 through 12 on the periodic table. In fact, the f-block lanthanide and actinide series are also considered transition metals and are called "internal transition metals". This definition of transition metals also includes elements from groups 3 through 12. In certain other independent embodiments, the transition metal or transition metal oxide comprises a Group 6, 7, 8, 9, 10, 11, or 12 element. In yet another independent embodiment, the transition metal or transition metal oxide is scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, Consists of palladium, platinum, copper, silver, gold or mixtures thereof. Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, and mixtures thereof are preferred dopants.

The following list of embodiments is intended to complement rather than replace or supersede the previous discussion.

Embodiment 1. Crystalline microporous germanosilicate composition designated CIT-14/IST with 8- and 12-membered ring channels

Embodiment 2. Powder X-ray diffraction (XRD) patterns of 7.59±0.5, 8.07±0.5, 12.88±0.5, 19.12±0.5, 19.32±0.5, 20.73±0.5, 22.33±0.5, 24.37±0.5, 27.19±0.5 and 27.69±0.5° The composition of crystalline microporous germansylate CIT-14/IST according to embodiment 1 characterized by having at least five characteristic peaks in 2-theta, wherein the composition comprises: Contains pure germanosilicate. In certain aspects of this embodiment, the CIT-14/IST germanosilicate composition comprises pure germanosilicate. In another independent aspect of this embodiment, the CIT-14/IST germanosilicate composition comprises one or more oxides of aluminum, boron, gallium, hafnium, iron, tin, titanium, vanadium, zinc, or zirconium. It comprises a framework containing In an independent aspect of this embodiment, the X-ray powder diffraction (XRD) pattern has at least five characteristic peaks with 5, 6, 7, 8, 9, or 10 of those characteristic peaks defined above. indicate a peak. In a separate aspect of this embodiment, peak position uncertainty is independently (for each peak) ±0.5 degrees 2-theta, ±0.4 degrees 2-theta, ±0.3 degrees 2-theta, ±0.2 degrees 2-theta, ±0.15 degrees 2-theta, or ±0.15 degrees 2-theta.

Embodiment 3. The crystalline microporous germanosilicate CIT-14/IST composition of embodiment 1 or 2, wherein the powder X-ray diffraction (XRD) pattern is 7.59±0.5, 8.07±0.5, 19.12±0.5, 20.73± 0.5, and 22.33 ± 0.5 degrees 2-theta, and optionally at least 3 characteristic peaks at 12.88 ± 0.5, 19.32 ± 0.5, 24.37 ± 0.5, 27.19 ± 0.5, and 27.69 ± 0.5 degrees 2-theta That's what I mean. Viewed as independent Aspects of this embodiment, the data in Table 1 above, and the comments associated with that table, are as follows.

Embodiment 4. The crystalline microporous germanosilicate CIT-14/IST composition of any one of embodiments 1-3, wherein 12:1 to 13:1, 13:1 to 14:1, 14:1 with Si:Ge ratios ranging from to 15.1. from 15:1, 15:1 to 16:1, 16:1 to 17:1, 17:1 to 18:1, 18:1 to 19:1, 19:1 to 20:1, or any of these aforementioned Any combination of two or more of the subranges, eg 14:1 to 18:1. Each of these ranges is considered an independent Aspect within this embodiment.

Embodiment 5. The crystalline microporous germanium according to any one of embodiments 1-4, wherein the crystals are orthorhombic and have a Cmmm space group, or a Cmcm space group, or an intracrystalline disorder of the two domains. Nosilicate CIT-14/IST compositions.

Embodiment 6. The crystalline microporous germanosilicate CIT-14/IST composition of any one of embodiments 1-5, having unit cell parameters.

[Table 6]

Embodiment 7. Any one of Embodiments 1 through 6, wherein the 8-membered ring channel has a pore size of about 3.3 A x 3.9 A and the 12-ring channel has a pore size of about 4.9 A x 6.4 A 2. The crystalline microporous germanosilicate CIT-14/IST composition of claim 1. In one aspect of this embodiment, the respective pore sizes are 3.26 Å×3.93 Å and 4.86 Å×6.44 Å. compression, etc.) or the ratio of Si:Ge may change these values. In some aspects of these embodiments, the average metal-oxygen (TO) bond length in the framework is in the range of 1.55-1.65 Å, the average oxygen-metal-oxygen (OTO) in the framework is 98 ^° -116 ^° , mean metal-oxygen-metal (TOT) in the range of 139 ^° to 180 ^° ].

Embodiment 8. 8. The crystal of any one of embodiments 1-7, which is derived or derivable from a reaction characterized as an inverse sigma transformation of a crystalline microporous germanosilicate designated CIT-13/OH. polycrystalline microporous germanosilicate CIT-14/IST compositions. Specific properties of CIT-13/OH are described in more detail elsewhere herein, and these descriptions are incorporated herein as though physically incorporated.

Embodiment 9. A crystalline microporous germanosilicate designated CIT-13/OH (described elsewhere herein) was heated at elevated temperature to the prefabricated microporous germanosilicate "-CIT-14" (also herein , which descriptions are also incorporated herein) with a concentrated aqueous mineral acid (e.g., as a dispersion of germanosilicate in aqueous acid) for a time sufficient to form The crystalline microporous germano-silicon CIT-14/IST composition of any one of embodiments 1-8.

In certain aspects of this embodiment, (a) the mineral acid is aqueous HCl or _HNO3 or an equivalent strong acid; (b) the concentration of the mineral acid ranges from 6 to 12M; (c) the elevated temperature is , a temperature in the range of 80 ^° C to 120 ^° C, preferably about 95 ^° C. (d) sufficient time ranges from 4 to 96 hours, preferably 4 to 24 hours; conditions corresponding to 95 ^° C. for 6 hours are suitable; Isolating the demanganized germanosilicate is the material designated "-CIT-14." Wash with water ⁽ preferably distilled or deionized water) until the ^pH is neutral; It further comprises heating at a temperature ramp rate of 1 ^° C./min for a time in the range of ˜12 hours, preferably 580 ^° C. for 6 hours.

Embodiment 10. 6.45 ± 0.2, 7.18 ± 0.2, 12.85 ± 0.2, 20.78 ± 0.2, 26.01 ± 0.2 and A crystalline microporous germanium silicate designated CIT-13/OH that exhibits a powder XRD (Xload Diffraction) pattern with at least 5 peaks at 26.68±0.2 degrees 2-theta. In some aspects of this embodiment, the peak at 6.45±0.2 degrees 2-theta is reduced in intensity (weaker) relative to the peak at 7.18±0.2 degrees 2-theta, the latter peak being the strongest in the pattern. (see Examples). In another aspect of this embodiment, the powder XRD pattern exhibits an additional peak at 11.58°±0.2° 2-θ. The data in Table 2 and the comments associated therewith are considered independent aspects of this embodiment.

This composition of CIT-13/OH germanosilicate, as well as its use in the preparation of CIT-14/IST, are considered independent embodiments of the present disclosure.

Embodiment 11. The crystalline microporous germanosilicate CIT-14/IST composition of embodiment 8 or 9 or the crystalline microporous germanosilicate CIT-13/OH of embodiment 10, wherein the crystals are CIT-13/OH The crystalline microporous germanosilicate of embodiment 8 or the crystalline microporous germanosilicate of embodiment 8 is prepared by a method comprising hydrothermally treating an aqueous composition obtained from a mixture of A crystalline microporous germanosilicate, which is brought into embodiment 9 or 9 by hydrothermally treating an aqueous composition obtained from the following mixture.
(a) It is a source of silicon oxide ( _SiO2 ).
(b) a source of germanium oxide ( _GeO2 ); and
(c) be any source of aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combinations or mixtures thereof;
(d) at least one hydroxide salt of a substituted benzylimidazolium organic structure director (OSDA) cation having the structure:

[Chemical 3]
(e) optionally, at least one compositionally matched seed crystal; and
(f) water.
under conditions effective to crystallize a crystalline microporous germanosilicate composition designated CIT-13/OH;
(a) Si:Ge molar ratio in the range of 2 to 4, preferably 2.
(b) Water with a water:Si molar ratio in the range of 8:1 to 12:1.
(c) water having a molar ratio of water:(SiO ₂ +GeO ₂ ) in the range of 6:1 to 7:1;
(c) containing hydroxide ions (OH) in a molar ratio of OH:(SiO ₂ +GeO ₂ ) in the range of about 0.3:1 to 0.7:1;
where the aqueous composition is essentially free of fluoride ions.

In an independent aspect of this embodiment

(1) The source of silicon oxide consists of silicates, silica hydrogels, silicic acid, fumed silica, colloidal silica, tetraalkyl orthosilicates, silicon hydroxide or combinations thereof (or equivalent sources), preferably is sodium silicate or tetraalkylorthosilicate, more preferably tetraethylorthosilicate (TEOS).

(2) The source of germanium oxide consists of GeO ₂ or its hydrated derivatives (or equivalent sources).

(3) Substituted benzylimidazolium organic structure directing agent (OSDA) cations have an OSDA:(SiO ₂ +GeO ₂ ) molar ratio in the range of about 0.3:1 to 0.7:1, preferably about 0.4:1 to 0.6: Must exist in the range of 1.

(4) The aqueous composition is essentially free of alkali metal cations, alkaline earth metal cations or diones, or combinations thereof.

(5) at least one substituted benzylimidazolium organic structure director (OSDA) cation has a structure;

[Chemical 4]

(6) Aqueous compositions are suspensions or gels.

(7) Effective crystallization conditions include subjecting the mixture to a temperature of about 140 ^° C. to about 180 ^° C., and for a time of about 4 days to about 4 weeks.

(7) Hydrothermally treat the aqueous composition in a rotary kettle.

(8) The method further comprising isolating the crystalline microporous germanosilicate solid composition.

Embodiment 12. The crystalline microporous germanosilicate CIT-14/IST composition of embodiment 8, 9, or 11, or the crystalline microporous germanosilicate CIT-13/OH of embodiment 10 or 11, wherein CIT-13 The /OH crystalline microporous germanosilicate is fluoride free and has at least d4R units, preferably with an average Ge atom per D4R unit of 4 or more, allowing Ge4 rings to be present in the d4R units. ing. A method for determining the average number of Ge atoms in a d4r unit is defined elsewhere and incorporated within this embodiment. In some independent aspects of this embodiment, the Si:Ge ratio is 3.5 to 3.6, 3.6 to 3.7, 3.7 to 3.8, 3.8 to 3.9, 3.9 to 4.0, 4.0 to 4.1, 4.1 to 4.2, 4.2 to 4.3, 4. to 4.3, 4. to 4.3, 4.1 to 4.1, 4. to 4.1, 4. to 5.0. in the range defined by 3 to 4.4, 4.4 to 4.5, 4.5 to 4.6, 4.6 to 4.7, 4.7 to 4.8, 4.8 to 4.9, 4.9 to 5.0, 5.0 to 5.2, or any two or more of the foregoing ranges , for example from 3.5 to 3.9. Each of these ranges is considered an independent Aspect within this embodiment.

Embodiment 13. The crystalline microporous germanosilicate CIT-14/IST composition of embodiment 8, 9, 11, or 12 or the crystalline microporous germanosilicate CIT-13/OH of any one of embodiments 10-12 is , optionally containing alkali metal cation salts, alkaline earth metal salts, transition metals, transition metal oxides, or combinations thereof. The properties of salts, metals, and metal oxides are discussed elsewhere in this specification and incorporated into this embodiment. In one aspect of this embodiment, each germanosilicate is in its hydrogen form. In another aspect of this embodiment, each germanosilicate contains one or more of salts, metals, or metal oxides within its pores.

Embodiment 14. The crystalline microporous germanosilicate CIT-14/IST composition according to any one of embodiments 1-9, 11-13, or the crystalline microporous according to any one of embodiments 10-13 A catalyst comprising the germanosilicate CIT-13/OH.

Embodiment 15. A process for influencing organic transformations or separating materials, said process comprising:
(a) Carbonylation of DME with CO at low temperature.
(b) reducing NOx with methane;
(c) cracking, hydrocracking, or dehydrogenating hydrocarbons;
(d) degreasing the hydrocarbon feedstock;
(e) converting paraffins to aromatics;
(f) isomerizing or heterogenizing the aromatic feedstock;
(g) alkylating the aromatic hydrocarbon;
(h) oligomerizing the alkene.
(i) aminate a lower alcohol;
(j) separating and sorbing lower alkanes from the hydrocarbon feedstock;
(k) isomerizing olefins;
(l) producing high molecular weight hydrocarbons from low molecular weight hydrocarbons;
(m) reforming hydrocarbons;
(n) conversion of lower alcohols or other oxygenated hydrocarbons to produce olefin products (including MTO);
(o) epoxidizing the olefin with hydrogen peroxide;
(p) reducing the content of oxides of nitrogen in the gas stream in the presence of oxygen;
(q) separating nitrogen from a nitrogen-containing gas mixture, or
(r) converting synthesis gas containing hydrogen and carbon monoxide into a hydrocarbon stream, or
(s) reducing the concentration of organic halides in the initial hydrocarbon product;
By contacting each feed with the catalyst of embodiment 14 under conditions sufficient to affect the named transformation.

Embodiment 16. The crystalline microporous germanosilicate CIT-14/IST composition of any one of embodiments 1-9 or 11-13 (or compositions designated as CIT-14/IST elsewhere herein) any) comprising contacting a crystalline microporous germanosilicate. An aqueous mineral acid designated as CIT-13/OH (or as described elsewhere herein) according to at least any one of embodiments 10-12 and an aqueous mineral acid (e.g., germano as a dispersion of silicates) at elevated temperatures sufficient to form the As-made microporous germanosilicate "-CIT-14" (again, as described elsewhere herein and so incorporated herein). contact only for time.

In certain aspects of this embodiment, (a) the mineral acid is aqueous HCl or _HNO3 or an equivalent strong acid; (b) the concentration of the mineral acid ranges from 6 to 12M; (c) the temperature rise is 80 ^° a temperature in the range of C to 120 ^° C., preferably about 95 ^° C.; Are suitable. Conditions corresponding to 95 ^° C. for 6 hours are preferred; (e) following contact with acid, the resulting demanganized germanosilicate is isolated as material designated "-CIT-14". (f) rinse the "-CIT-14" material with water (preferably distilled or deionized water) until the wash is pH neutral;

Embodiment 17. The method of embodiment 16 comprises drying the as-manufactured and washed "-CIT-14" composition for a time and temperature sufficient to form a crystalline microporous germanosilicate CIT-14/IST composition. Further comprising baking. In an independent aspect, these conditions include subjecting this separated and washed "-CIT-14" material to a temperature ranging from about 450 ^° C. to 650 ^° C. for a time ranging from 2 hours to 12 hours. Further comprising heating, preferably at 580 ^° C. for 6 hours, more preferably at a temperature ramp rate of 1 ^° C./min.

The disclosure also encompasses those embodiments of CIT-13/OH germanosilicates prepared by the hydroxide route as specifically described herein. The present disclosure also provides CIT-13/OH characterized as having d4r units containing an average of at least, preferably 4 or more Ge atoms per d4r, allowing for the presence of Ge-4-rings in the d4r units. Also included are those embodiments of germanosilicates. The present disclosure also encompasses those embodiments of CIT-13/OH germanosilicates that exhibit previously unobserved reactivity characteristics that are the result of the new and unique physical characteristics defined herein. do.

Examples The following examples provide experimental methods used to characterize these novel materials and variations thereof, and illustrate some of the concepts described within this disclosure. Although each example, both provided here and elsewhere in the text of this specification, is believed to provide specific individual embodiments of compositions, methods of preparation, and uses, None of the examples should be considered limiting of the more general embodiments described herein.

Unless otherwise specified, powder XRD patterns, nmr-spectra, or other representations of structures shown herein for particular compositions are believed to be representative of those attributed to the general structure to which they relate. .

In the following examples, efforts have been made to ensure accuracy with respect to numbers used (eg amounts, temperature, etc.) but some experimental errors and deviations should be accounted for. Unless indicated otherwise, temperatures are in ° C. and pressures are at or near atmospheric.

Example 1. experiment

Example 1.1. Material preparation

CIT-13 from a fluoride-free gel (denoted as CIT-13/OH) was treated with 1,2-dimethyl-3-(2-methylbenzyl)imidazolium hydroxide (denoted as “orthomethylbenzyl”) or 1,2-Dimethyl-3-(3-methylbenzyl)imidazolium hydroxide (denoted as "metamethylbenzyl"), crystallized using them as OSDAs, they are CIT-13 is the same as getting Synthetic protocols for the two OSDAs are provided elsewhere. The gel composition ratio is x/(x+1) _SiO2 :1/(x+1)GeO2:0.5ROH: _yH2O , where x is the Si/Ge ratio of the gel and y is _{the H2O} of the gel. /(Si+Ge) ratio. Preferred values for x and y are shown below. The detailed procedure and gel composition are as follows. CIT-13/OH samples are denoted as CIT-13/OH[z], where z represents the Si/Ge ratio of CIT-13 crystals measured using energy dispersive spectroscopy (EDS).

CIT-13 from a conventional fluoride-containing gel (denoted CIT-13/F) was also prepared for comparative analysis with CIT-13/OH and was based on previously reported methods. As with the CIT-13/OH samples, the CIT-13/F samples are denoted as CIT-13/F[z], where z denotes the crystalline Si/Ge ratio measured using EDS.

IM-12 samples were also prepared according to protocols previously reported in the literature for comparison with CIT-13. Similar to CIT-13, the IM-12 sample is also denoted as IM-12[z] (z=EDSSi/Ge ratio).

Example 1.2. Detailed Synthesis of CIT-13/OH

In the final stage of gel preparation, the desired water level should be adjusted based on the total weight (liner + stir bar + gel), so the dry weight of the liner and stir bar should be characterized.

Germanium dioxide (99.999%, Strem) was completely dissolved in the OSDA solution in a 23 mL PTFE liner for a Parr steel autoclave. 1,2-dimethyl-3-(2-methylbenzyl)imidazolium hydroxide and 1,2-dimethyl-3-(3-methylbenzyl)imidazolium hydroxide were used as OSDA for CIT-13/OH. Methods for preparing these OSDAs are known. The desired amount of TEOS was added to the solution and the mixture was stirred overnight until the TEOS phase was completely hydrolyzed. Excess water and ethanol were allowed to evaporate under a stream of air at room temperature until the gel was thick and viscous. Ethanol, a hydrolysis product of TEOS, appears to adversely affect both crystallization rate and product purity. To maximize the extent of ethanol removal, purified water (approximately 10 mL) was added to the viscous gel and evaporated again with stirring until the gel became viscous. This water addition-evaporation step was repeated a total of 5 times. (Note: This ethanol removal step is not necessary if fumed silica was used as the Si source). Finally, the desired moisture content was adjusted based on the above total weight (liner + stir bar + gel). The final gel composition is x/(x+1) _SiO2 :1/(x+1)GeO2:0.5ROH: _yH2O , where x is the Si/Ge ratio of the gel and y is the _H2O / (Si+Ge) ratio. The values of x and y are as shown in Table 4. Optimized ranges for x and y are given in the text. CIT-13 seed crystals (5 wt% relative to the total weight of _SiO2 + _GeO2 ) were added as needed. The gel was sealed in a steel autoclave and placed in an oven preheated to the desired temperature.

After 1 week of crystallization, the gel was removed. After the first week of crystallization, the gel usually turned dark brown and solidified. A clean, hard PTFE rod was used to thoroughly grind the solidified gel into a powder. The crushed gel was placed back into the oven and crystallization resumed. Aliquots were taken weekly to monitor the extent of crystallization. The final product was washed repeatedly with distilled water and acetone and dried in a 100°C convection oven.

Gel compositions, crystallization conditions, and corresponding results are summarized in Table 4.

[Table 7]
Table 4. Summary of synthesis conditions and results of fluoride-free CIT-13/OH

Example 1.2. Germanosilicate conversion and post-synthetic modification of CIT-13/OH to CIT-14/IST
Conversion of CTH to CFI was performed by exposing freshly calcined CIT-13/OH samples to a moisture-bearing atmosphere. Here, only one condition (30% relative humidity at 25° C. (pH ₂ O=7.1 Torr)) was used to ensure consistency with results from previous work. The extent of metamorphosis was monitored based on PXRD. Based on the weakly acidic ADOR type conversion of CIT-13/F and the inverse sigma type conversion of CIT-13/OH, CIT-14/ESP (ESP is ethoxysilylated pilling) and CIT-14/IST (IST is inverse sigma type conversion). ) were prepared respectively. Inverse sigma conversion of CIT-13/OH was performed by treating freshly calcined CIT-13/OH with 12M HCl at 95°C for 48 hours. The resulting solid ("-CIT-14") was recovered using a centrifuge and washed repeatedly with distilled water until the pH became neutral. IST means inverse sigma transformation, and the final material CIT-14/IST was obtained by heating to 580 °C for 6 h at a heating rate of 1 °C min ^-1 . The UTL-to-OKO inverse sigma transformation was also carried out using the -12 sample. A SEM image of the CIT-14/IST sample is shown in Figure 4(AB). 4(AB).

Degarmentation and fluorination of germanosilicates were performed for ¹⁹ Fmagic-anglespinning (MAS) and ¹ H- ²⁹ Sicross-parolarization (CP) MAS NMR studies. Cold water degunning of the calcined germanosilicate was performed as follows. 100 mg of freshly calcined germanosilicate was immersed in 100 mL of distilled water at room temperature and stirred overnight. The resulting solid was collected using a centrifuge and washed repeatedly with distilled water. The degreased samples were vacuum dried at room temperature. Post-synthetic fluorination of germanosilicates crystallized in a fluorine-free medium was carried out as follows. 100 mg of as-prepared CIT-13/OH was pulverized with 20-25 mg of ammonium fluoride and heated at 150°C for 24 hours. Excess ammonium fluoride was removed by washing with cold distilled water and the recovered solid was dried at 100°C.

Example 1.3. Characterization

Powder X-ray diffraction (PXRD) profiles were collected using a Rigaku Miniflex II diffractometer (CuKα radiation λ=1.5418 A). High-resolution PXRD data were collected at the 2-1 powder diffraction beamline at the Stanford Radiation Light Source (SSRL) using a wavelength of 0.9998A. For high-resolution PXRD experiments, calcined CIT-14 powder samples were packed and sealed in 1.0 mm glass capillaries.

Scanning electron microscopy (SEM) images and elemental analysis data were collected on a ZEISS1550VP field emission (FE)-SEM microscope equipped with an OxfordX-maxSDDEDS system. Solid state magnetic resonance (MAS) spectra were acquired using a BrukerAvance 500MHz (magneticfield=11.2T). Molecular sieve samples were loaded into a 4 mm diameter zirconia rotor with a Kel-FR cap. ¹ H- ¹³ C cross-polarized (CP) MAS spectra, ²⁹ SiMAS spectra, and ¹ H- ²⁹ SiCPMAS spectra were collected at a MAS spin rate of 8 kHz and ¹⁹ FMAS spectra at 12 kHz.

Example 2. Results and Discussion

Example 2.1 Synthetic Considerations

CIT-13 can be crystallized in hydroxide media by omitting fluoride and changing other gel compositions from those of the fluoride route of CIT-13. Unlike CIT-13/F, which could be crystallized in a medium to high range of gel compositions, CIT-13/OH is obtained in a much narrower range of gel compositions. The range of gel Si/Ge ratio and gel _H2O /(Si+Ge) ratio is 2<Si/Ge<4 and 6<H2O/(Si+Ge) when OSDA/(Si+Ge)=0.5. <7, preferably 2.5<Si/Ge<3.0 and 6.0<H2O/(Si+Ge)<6.5 respectively. Amorphous germanosilicates and unknown dense phases were obtained with gel compositions outside this compositional range. Crystallization of pure CIT-13 phase was observed at temperatures of 160°C and 175°C. Details of the synthesis (eg gel composition) are shown in Table 4. CIT-13/OH had a plate-like crystal morphology, as shown in Fig. 5(AC), and was similar to CIT-13 obtained from fluorine-containing preparations and equivalent structural germanosilicates. . The ¹ H- ¹³ CCPMAS spectrum of as-prepared CIT-13/OH[4.33] and the solution-phase ¹³ CNMR of OSDA (Fig. 6) show that the structure of OSDA is retained during the crystallization of CIT-13/OH. It was confirmed that The same off-the-shelf ¹ H- ²⁹ SiCPMAS spectrum also confirmed the presence of connectivity defects that compensated for the absence of fluoride. (Fig.7)

The PXRD profiles of as-prepared CIT-13/OH[3.88] and calcined CIT-13/OH[4.33] are displayed in Figure 8 (B-E). Other PXRD patterns are provided in FIG. All PXRD profiles were obtained under ambient conditions. The positions of the diffraction peaks agreed well with those of the reference CIT-13/F shown in FIG. 8(F). However, there is a difference in peak intensity between CIT-13/F and CIT-13/OH. Except for the sole CIT-13/OH[3.88] crystallized using ortho-methylbenzyl OSDA (Figs. 8(A) and 9(B)), other as-prepared CIT-13/OH[3.88] synthesized from meta-methylbenzyl OSDA 13/OH showed a very weak (200) peak at 2θ=6.44°, as shown in FIGS. 8(D) and 9(A). It shows a very weak (200) peak at 2θ=6.44°, as shown in 9(C-K). This weak (200) peak became stronger after OSDA was removed by calcination. (Fig. 8(E)) Moreover, some of the CIT-13/OH exhibit a distinct (310) peak at 2θ = 11.58°, as shown in Figs. 9(D-G) and 9(E). ing. A distinct (310) peak is shown at 2θ=11.58° as shown in 9(D-G) and 9(I-J). It can be seen that these (310) diffractions are attenuated by insertion after synthesis of fluoride using ammonium fluoride. Fluorination of CIT-13/OH also increased the intensity of the (200) peak. (Fig. 10) Thus, the absence of fluoride and the presence of the metamethylbenzyl OSDA cation within the CIT-13 backbone is responsible for the weak intensity of the (200) peak and the occasional appearance of the (310) peak. It seemed so.

The argon physisorption isotherm of CIT-13/OH[3.56] obtained at 87.45 K is superimposed with that of CIT-13/F[4.18] and shown in FIG. 8(G) for comparison. The micropore volume of CIT-13/OH[3.56] was 0.141 cc/g from the t-plot method (0.202 cc/g from the Saito-Foley method). This microporosity was slightly lower than the reference CIT-13/F [4.18] (deBoert-plot: 0.172 cc/g; Saito-Foley: 0.223 cc/g). A characteristic two-step adsorption due to the presence of 10MR and 14MR of CIT-13 (indicated by ↓ in FIG. 8(G)) was also observed for CIT-13/OH as expected.

Example 2.2. Consider converting CTH to CFI

CIT-13 type germanosilicate, unlike other d4r type germanosilicates such as UTL, IWW and ITH, slowly changed to CFI type germanosilicate when exposed to ambient moisture (*CTH to CFI conversion). This change was caused by the rearrangement of Ge-rich d4r units into dzc units due to instability of the CIT-13 framework caused by the presence of germanium-rich d4r units and the crystallographic nature of the CFI layer. Interestingly, CIT-13/OH was shown to convert to the corresponding germanosilicate CIT-5 faster than CIT-13/F of comparable germanium content. CIT-13/OH[4.33] converted to CFI within 12 days, while CIT-13/F[4.31] was completely converted to CFI-type germanosilicate over 85 days. Fig. 11(A) and Fig. 11(B) show the PXRD profile of the sintered body after exposing CIT-13/OH[4.33] to normal humidity (pH2O = 7.1 torr, relative humidity 30%, 25°C) for a certain period of time. It was shown to. 11(A) and 11(B). The (400) peak of CIT-13 initially overlapped with the (002) diffraction at 2θ=13.07°, but after 2 days it shifted to 2θ=13.69° and became separate. After 8 days, three characteristic diffractions of the CFI framework ((301), (002), (400)) began to appear. The PXRD profile after 10 days of environmental exposure was in good agreement with that of reference pure silica CIT-5. The time-dependent position of the cfi-cfi interlayer distance estimated from the (200) diffraction position is shown in Fig. 11(E) for CIT-13/OH[4.33] and CIT-13/F[4.31]. It indicates that the transformation of CIT-13/OH is faster than that of 13/F.

For CIT-13/F, it was found that decreasing the Si/Ge ratio from 4.31 to 3.87 reduced the time required to achieve complete transformation from about 4 months to 12 days. This acceleration of the conversion rate may be due to an increase in germanium sites within the d4r unit, the structural building unit that converts to the dzc unit of the CFI framework. As in the case of CIT-13/F, decreasing the Si/Ge ratio of CIT-13/OH further accelerated the conversion of *CTH to CFI. CIT-13/OH[3.88] transformed into the corresponding CIT-5 type German silicate within 2 days as shown in the figure. As shown in 11(C) and 11(D), it converted to the corresponding CIT-5 type germanosilicate within 2 days. This was at least six times faster than the similar transformation using CIT-13/F[3.87]. To investigate the environment of Si sites in these germanosilicates, ²⁹ SiNMR spectra of calcined CIT-13/OH[3.88] and the resulting Ge-CIT-5 were obtained (Fig. 12). Similar to CIT-13/F, CIT-13/OH showed three groups of signals at -104.2, -109.4 and -113.9 ppm. This spectral shape was consistent with previously reported CIT-13 (see Figure 3 above) and related substances synthesized in fluoride media. Ge-CIT-5 derived from CIT-13/F showed a single broad signal at -110.61 ppm, whereas Ge-CIT-5 derived from CIT-13/OH[3.88] at approximately -109.0 and -112.2 ppm. shows two separate groups of peaks. The disappearance of the −104.2 ppm shoulder in the spectrum of CIT-13 is attributed to the rearrangement of the d4r unit to the dzc bridging unit also seen in the conversion of CIT-13/F. Therefore, these signals have the same origin as the -113ppm and -115ppm signals of pure silica CIT-5 and can be assigned to the sulfur layer Si site.

Based on the fact that the higher germanium content of the parent CIT-13 resulted in faster conversion of *CTH to CFI, CIT-13/OH crystals with similar Si/Ge ratios were found to be similar to CIT-13/F crystals. can be inferred to have more germanium in its d4r unit compared to . In CIT-13/F, it was confirmed that the cfi layer also has a non-zero germanium occupancy. The formation of d4r units is known to be promoted by the presence of fluoride anions, which can stabilize the low framework T-O-T angle, and high germanium content. Formation of the d4r-type CIT-13 framework in the absence of fluoride is thought to result in increased incorporation of germanium into the d4r unit. In fact, the CIT-13/OH sample with low Si/Ge ratio underwent inverse sigma transformation in concentrated acid to give "-CIT-14", an analogue of COK-14 derived from IM-12. Such a transformation strongly suggests the presence of many clustered germanium sites within the d4r unit and the presence of pure Ge-4 rings.

Example 2.3. Consideration of Topotactic Conversion from CIT-13 to '-CIT-14' and CIT-14/IST
Despite the structural similarities between CIT-13 and IM-12, the elution of Ge-4-rings from *CTH-type germanosilicates by strong acids has not yet been reported. Unlike IM-12, it is suggested that the Si-O-Si interlayer cross-linking of *CTH-type germanosilicates is the main obstacle to such transformation. ADOR conversion of SAZ-1 to IPC-16 and Pawley purification of IPC-16 have emerged. Most recently, it was reported that the T-site within the d4r unit of CIT-13/F was partially removed by mild base treatment, resulting in ECNU-23. However, the presence of pure Ge-4-rings in the d4r unit is essential for true inverse sigma conversion by strong acids, and IM-12 is the only d4r-type with such structural and elemental prerequisites. German silicate.

Ge-rich CIT-13 crystallized in a hydroxide medium undergoes a structural transformation that can be explained by the inverse sigma transformation, in which the Ge-4-ring is simultaneously removed from the d4r, as schematically shown in Fig. 13(A). can be caused. Two examples (CIT-13/OH[3.71] and CIT-13/OH[3.56]) were demonstrated here based on the PXRD profile shown in FIG. 13(B). Following the nomenclature used by Verheyen (Nat. Mater. 2012, 11, 1059), the material that has just been acid treated before calcination is denoted as "-CIT-14". Although no Rietveld refinement was performed for “CIT-14”, the unit cells in the interlayer direction (i.e., a direction) after firing of “-CIT-14”, similar to the condensation of -COK-14 to COK-14 A small decrease in parameters was observed. Presence or absence of fluoride and germanium content were found to be the two most important synthetic factors for the preparation of CIT-13 germanosilicate from which CIT-14 can be obtained by inverse sigma transformation. Treatment of calcined CIT-13/F[3.87] with 12M HCl did not give "-CIT-14" despite its high germanium content. A similar treatment of CIT-13/OH[4.33] yielded a disordered layered material. (Fig.14(A-B))

For comparison, an isostructural material was obtained based on the conventional ADOR transformation of CIT-13, denoted here as CIT-14/ESP. This conversion was similar to that of SAZ-1 to IPC-16. The PXRD profile of CIT-14/ESP from the ADOR conversion of CIT-14/IST and CIT-13/F[4.33] prepared by treating calcined CIT-13/OH[3.56] with 12M HCl is shown in the figure. rice field. Shown in 15(A) and 15(B) together with that of the reference CIT-14 model based on the GULP geometry optimization algorithm. Apparently, the intensity of the (200) interlayer diffraction of CIT-14/IST was stronger than that of CIT-14/ESP. This difference in diffraction intensity is attributed to the elemental composition of the single four-ring (s4r) bridging unit of CIT-14. The effect of germanium occupancy at the seven T-sites of CIT-14 on the (110) and (200) diffraction intensities was calculated and the results are shown in FIG. As a result, we find that the relative intensity of the (110) diffraction of PXRD increases significantly when the two T-sites (T3 and T7) are occupied with germanium. T7 is the s4r site and T3 is the site directly adjacent to the d4r site. In fact, the Rietveld refinement of CIT-14/IST indicates that the germanium content of T7 is 21%, accounting for 52% of the total skeletal germanium population. (Table 5, supra). No significant germanium occupancy was detected for T3. Considering that the inverse sigma transformation displaced the pure Ge-4 ring from the d4r unit of the parent germanosilicate, the d4r unit of CIT-13/OH has on average more than four germanium atoms. It can be concluded that there are However, no significant difference was found between the ¹ H-decoupled ²⁹ SiMAS spectra of CIT-14/IST and CIT-14/ESP (Fig. 15(D). This spectral similarity is presumed to be due to the presence of residual germanium sites in the CIT-14 backbone, and very little Q3-type silanol was detected.

As mentioned above, CIT-14/IST had a higher germanium content than CIT-14/ESP. The EDSSi/Ge ratios of two CIT-14/IST samples derived from CIT-13/OH[3.56] and CIT-13/OH[3.71] were found to be 14.5 and 17.5, respectively. These values are lower than those of the CIT-14/ESP samples (Si/Ge=50-253, depending on the degree of degreasing, see Fig. 17) subjected to degreasing stripping using a weak acid (0.1M HCl). . The Si/Ge ratios of the COK-14 samples prepared this time using the same procedure for the two IM-12 samples (Si/Ge=3.80and4.79) are 17.5 and 29.2, which are in line with the values reported by Verheyen et al. 110) much lower. These values were much lower than those of IM-12's ADOR product, IPC-2 (reported as Si/Ge=97), which underwent weak acid exfoliation similar to CIT-14/ESP. These results support that the strong acid inverse sigma transformation leaves extra germanium sites (other than Ge-4-ring exfoliation) in the d4r unit uneluted.

Microporousity of CIT-14 was investigated using an argon adsorption isotherm acquired at 87.45K. (FIG. 20) CIT-14/IST showed no adsorption-desorption hysteresis, while CIT-14/ESP gave a desorption curve that clearly deviated from its adsorption curve. A similar hysteresis was also observed from IPC-2 formed by the ADOR-type pillaring method. This microscopic mesology is commonly observed in post-synthetic treatments in nitric acid media. In addition, the specific pore volume of CIT-14/IST (0.105 cc/g from t-plot, 0.141 cc/g from Saito-Foley) is that of CIT-14/ESP (0.065 cc/g from t-plot, Saito -102 cc/g) than Foley. A similar trend is observed in the conversion from UTL to OKO. Also, as clearly seen in Fig. 20(B), CIT-14/IST is p/p ₀ = about 1 × 10 ^-4 lower than CIT-13 (p/p ₀ ~ 3 × 10 ^-4 ). It was found to begin to adsorb argon. This adsorption onset pressure is very similar to 8MR ring zeolite A (LTA) (p/p ₀ ~1×10 ^-4 ). Therefore, argon adsorption of CIT-14 was initiated by adsorption into its 8MR pores.

The decrease in pore volume with inverse sigma transformation from CIT-13 to '-CIT-14' was investigated theoretically and experimentally. For theoretical evaluation, the utility TOTOPOL for topological analysis developed by Treacy and Foster was used to estimate the pore volume reduction. Crystallographic information (cif) files obtained from the Rietveld refinement of CIT-13 and CIT-14/IST (this study, videinfra) were used as the computational framework model. The results are summarized in Table 6. The experimentally observed decrease in micropore volume (Saito-Foley: 30.2%; t-plot: 25.5%) was similar to or less than the value estimated using TOTOPOL (30.2%), but TOTOPOL may underestimate the pore volume of CIT-13 and CIT-14 compared to the experimentally obtained values.

[Table 8]
*Theoretical unit cell was calculated using the EDS elemental composition of CIT-13/OH[3.56] and its CIT-14/IST. It was estimated directly from the argon physisorption isotherm shown in FIG.

Since the position of the bridging site, i.e., the stratum site directly connected to the d4r or s4r unit of CIT-13 or CIT-14, respectively, did not change during the inverse sigma transformation, CIT-14/IST was transferred from its parent CIT-13 to It should have directly inherited the chaotic pattern. Indeed, the (111) and (201) diffraction peaks estimated to be located at 2θ=11.43° and 11.78°, respectively, by the disorder model based on the GULP algorithm were not observed in the actual PXRD pattern of CIT-14/IST. . (Fig. 15(C)) These diffractions were also not observed in CIT-14/ESP, consistent with the previously reported ADOR conversion of SAZ-1 to IPC-16. However, in the ADOR conversion, the Ge-rich d4r is completely removed by exfoliation in mild acid and the bridging s4r is formed by the introduction of novel silicon sources such as diethoxydimethylsilane. Therefore, the disturbance pattern of CIT-14/IST may not be identical to that of CIT-14/ESP or IPC-16.

XPD patterns could be indexed in the orthorhombic unit cell (a=21.90 A, b=13.74 A, c=10.11 A) using the program TREOR35 implemented in the software CMPR36. The initial CIT-14 structural model was derived from the CIT-13 structure (assuming all silica) by inverse sigma transformation,20 and no disturbances from CIT-13 were introduced. In addition, the DLS-7637 program was used to optimize the geometry, assuming the same space group Cmmm as the parent CIT-13 (*CTH). Using this as a starting point, Rietveld refinement using TOPAS was performed. The final structure of CIT-14/IST was obtained by Rietveld refinement of the powder pattern with agreement values R _F =0.057, R _wp =0.078, R _exp =0.053 (FIG. 21(A)).

Since all symmetry elements are preserved, the inverse sigma transform satisfies the IUPAC definition of a topotactic transform. The idealized structure and pore system of CIT-14/IST are displayed in Figures 21(B) and 21(C), respectively. CIT-14/IST is a two-dimensional channel system bounded by 12MR and 8MR pores, with limiting dimensions of 6.4×4.9A and 3.9×3.3A, respectively. Similar to ferrierite (FER), CIT-14/IST has a small cage that is connected to two adjacent straight main channels through small holes. On the other hand, EON and MOR, known as two-dimensional 12/8MR topologies, do not have such a cage structure. Due to the presence of disorder (illustrated in FIG. 21(D)), the 8-MR subchannels are not linear. The unit cell parameter c can also be defined as c'=c/2=5.0569A for the average structure, but no improvement in refinement was observed with smaller unit cells (i.e. atomic coordinates and profile change in the goodness of fit is minimal, but the number of parameters to be refined increases). Detailed crystallographic information for CIT-14/IST is provided in Tables 5 and 7 and FIG.

[Table 9]
Table 5. Crystallographic data. CIT-14/OH(*.ciffile) is a structure solution obtained by Rietveld refinement by synchrotron powder X-ray diffraction.

[Table 10]
Table 7. Crystallographic data. Structural and compositional analysis of CIT-14/IST

Example 2.4. Consideration of Ge sequences within the d4r unit

The inverse sigma transformation properties of d4r-type germanosilicates can indirectly provide evidence for the existence of layer-parallel pure Ge-4 rings (d4r units). As mentioned in the previous section, Ge-rich CIT-13/OH (Si/Geratio<3.7) undergoes inverse sigma transformation similar to IM-12, and CIT-14/OH has high crystallinity and a clear pore system. Became an IST. PXRD and structural refinement also revealed that the remaining s4r unit of CIT-14 has a germanium site. Therefore, the elemental composition of the d4r unit of CIT-13/OH is [Si _n Ge _8-n ]-d4r (n<4) at low Si/Ge ratios, with four Ge completely flanking the d4r. presumed to occupy. Although CIT-13/F could be converted to CIT-14/ESP using the ADOR strategy, we were unable to achieve inverse sigma conversion with it. Furthermore, as noted above, CIT-13/OH showed much higher conversion of *CTH to CFI than CIT-13/F samples with similar germanium content. These results indicate that the presence or absence of fluoride, which can also direct and stabilize the structure of the d4r unit, plays a major role in arranging the elemental composition and distribution within the d4r unit of the super-large-pore germanosilicate CIT-13. ing.

¹⁹ FNMR spectroscopy can be used as a tool to reveal the elemental composition of small cyclic building blocks such as the d4r unit. Germanosilicates, which do not incorporate fluoride anions in direct synthesis, can be modified either as such or to demanganized backbones by inserting fluoride after synthesis. Fluoride-introduced d4r-type germanosilicate shows three signals at about -8 ppm (broad), -19 ppm (sharp), -38 ppm (sharp), [Si ₄ Ge ₄ ]-d4r, [Si ₇ Ge]-d4r and [ _Si8 ]-d4r. There is general agreement on the latter two allocations. However, the nature of the former -8 ppm peak, which is usually broad and sometimes accompanied by one or two shoulder signals, is still questionable due to the many possibilities in the placement of germanium.

The ¹⁹ F NMR spectra of the ready-made CIT-13/F and fluorinated CIT-13/OH samples are shown in Figure 23(AC). All CIT-13 samples show a broad peak centered around -8ppm, with no signal at -19ppm and -38ppm, indicating that the d4r units in these CIT-13 samples are rich in germanium. . Also, post-synthetic fluorination of CIT-13/OH revealed a sharp signal with multiple spinning sidebands at -123.7 ppm, presumably derived from surface ¹⁹ F-Si species due to surface etching. . This surface etching did not result in structural degradation, as also supported by the PXRD profile (Fig. 10). The -8ppm signal of CIT-13 is broader than that of IM-12, indicating that the germanium sequences within the d4r unit of CIT-13 are higher than those of fluorinated IM-12, regardless of the type of mineralizer used. also appear to be non-uniform. The -8ppm signal of CIT-13 was resolved into two peaks. Line 1 (-7.3 to -8.3 ppm) and Line 2 (-11.0 to -11.7 ppm). As shown in Figs. 23(A) and (B), CIT-13/OH[4.33] (16%) is higher than CIT-13/F[4.33](1 %) gave a stronger line 2 signal. This result indicates that the absence of fluoride in CIT-13 synthesis did indeed affect the placement of germanium sites within the d4r unit. CIT-13/OH[4.33] changes to Ge-CIT-5 faster than CIT-13/F with the same Si/Ge ratio, and this conversion from *CTH to CFI is caused by hydrolysis of the TO-Ge bond. It was shown above that IM-12 with Ge-O-Ge bonds collapsed very quickly (within a day) when exposed to room temperature. Kasian et al. showed that fluorinated IM-12 exhibited a shoulder peak at -12 ppm next to the main peak at -8 ppm (the -3 ppm shoulder peak observed for fluorinated IM-12 was detected in CIT-13). It has not been). This suggests that the origin of the Line 2 signal in CIT-13/OH is due to the highly clustered germanium site arrangement within the d4r unit such as the Ge-4-ring.

The 19F spectrum of CIT-13/OH[3.56] further increased the contribution of Line 2 (23%) and inverse sigma transformed to CIT-14/IST (as shown in Figure 23(C)). We also investigated the 19F NMR spectra of a series of STW-type germanosilicates ranging from pure silica to pure germania and found that decreasing the Si/Ge ratio from 5 to 0 resulted in a shift of the 19F main signal from -7.5 ppm to -10.5 ppm. 42 Still others have reported the presence of an upfield signal at -14 ppm in the ¹⁹ FNMR spectrum of Ge-rich ITQ-21 material. With these results in mind, we attribute the high field signal like line 2 to the high germanium content within the d4r unit.

The placement of germanium sites within the d4r unit of CIT-13/OH was further investigated based on the ¹ H- ²⁹ SiCPMAS NMR spectrum (FIG. 24) of the related germanosilicate demanganized using distilled water. It is speculated that this type of treatment removes most of the germanium sites from the d4r units, with concomitant conversion of adjacent silicon sites to silanol sites. CIT-13 and IM-12 water vapor desorption treated samples commonly show a strong Q3 signal in addition to a fully connected Q4 signal. A major difference between the samples was the intensity of the Q2-type (geminal) silanol signal. The demanganized samples of IM-12 (Si/Ge = 4.89 and 4.23) exhibited the weakest Q2 signal among the demanganized materials studied, consistent with previous observations by others. These samples were more Ge-rich than IM-12 (Si/Ge=5.3), in which inverse sigma transformation was confirmed. The Q2 signal signature in their ¹ H- ²⁹ SiCPMAS spectrum is believed to be due to excessive de-gunning. Unlike IM-12, the four CIT-13 samples shown in Figure 24 gave a moderately intense Q2 signal. Of CIT-13, only CIT-13/OH[3.71] underwent inverse sigma transformation to become CIT-14/IST, and the weakest Q2 signal was observed among CIT-13. The two CIT-13/F samples gave stronger Q2 signals than CIT-13/OH[4.33] regardless of the Si/Ge ratio. These CIT-13/F samples did not convert to CIT-14 by inverse sigma transformation as shown above. We also found that the ¹ H- ²⁹ SiCPMAS spectra of their demanganized products were similar to those of ITH and IWW in terms of their strong Q2 signals. This further supports the premise that the presence or absence of fluoride in the synthetic gel of CIT-13 affects the placement of germanium within the d4r bridging unit.

Three example types of germanium sequences (I, II, and III) and two Ge Richer sequences (II-2 and III-2 with 5 and 6 Ge sites, respectively) within the Si4Ge4 _{] -d4r} unit are It is illustrated in FIG. Based on their computational results, Corma et al. found that among the possible [Si4Ge4]-d4r configurations of AST germanosilicates, the alternating Si and Ge sites within the d4r unit (i.e., the Type I configuration) is the most energetic. proved to be advantageous for This germanium sequence has been suggested by Liu et al. to be present in CIT-13/F. Types II and III are [Si ₄ Ge ₄ ]-d4r sequences suggested to be present in ITH/IWW and UTL, respectively, in fluorinated and degelling ITQ-13, ITQ-22 and IM-12. Based on ¹⁹ FMAS and ¹ H- ²⁹ SiCPMAS spectra. 28. Most importantly, the Type III configuration can explain the extraction of the Ge-4-ring during the inverse sigma transformation of IM-12 and the high Si/Ge ratio of the resulting COK-14 material.

As for CIT-13/F, it has been pointed out that the existence of Si-O-Si bridges may inhibit the complete exfoliation of the cfi-type layered materials under acidic media. Moreover, CIT-13/F was not transformed into CIT-14 by strong acid treatment as described above. This result suggests that there is no pure Ge-4-ring in the d4r unit of CIT-13/F. Although very slow, CIT-13/F converted completely to Ge-CIT-5 when exposed to ambient humidity. This transformation mechanistically involves hydrolysis of the TOT bond parallel to the major 14MR channel within the d4r unit. Therefore, CIT-13/F cannot have Si-O-Si bonds along the main channel direction of d4r. Therefore, the configuration of type I or type II-2 (when Ge-rich) may explain all the transformation behavior exhibited by CIT-13/F. However, according to DFT-based calculations by Camblor et al., highly clustered germanium sites such as type II-2 may lead to a large contribution of the line 2 signal in its ¹⁹ FNMR, but this is not the CIT- Not observed at 13/F (see Fig. 23(A)). Therefore, CIT-13/F may have a Type I or other possible arrangement that could explain its transformation behavior.

As shown in Figures 23(B) and 23(C), the fluorinated form of the CIT-13/OH sample has a broader −8 ppm signal (line 1) and extra upfield than those of IM-12,28. showed a 16-23% contribution of the signal (line 2). These data suggest the presence of highly clustered germanium sites such as TypeII-2 and TypeIII-2 within the d4r unit. Also, the fast *CTH-CFI conversion of CIT-13/OH can be explained by Ge-O-Ge bonds parallel to the channel direction. The type III-2 configuration is consistent with the presence of pure Ge-4 rings at the s4r sites of CIT-14/IST and the high germanium content. Indeed, our fine structure solution obtained from synchrotron PXRD confirms that the Si/Ge ratio of the bridging s4r unit is about 4, which is pure Ge within the d4r unit of CIT-13/OH. Implying that there are 1 or 2 additional germanium substitutions on the 4-ring. Therefore, we suggest that clustered germanium sites like type II-2 or type III-2 are obtained in the absence of fluoride in the synthetic gel of CIT-13.

As those skilled in the art will appreciate, numerous modifications and variations of the present invention are possible in light of these teachings, and all such are contemplated herein. All documents cited herein are hereby incorporated by reference for their teachings at least in the context provided.

Claims (18)

A crystalline microporous germanosilicate composition designated as CIT-14/IST having 8- and 12-ring channels and having at least 5 characteristic peaks at 7 in a powder X-ray diffraction (XRD) pattern. A crystalline microporous germane silica composition, characterized by comprising: 59±0.5, 8.07±0.5, 12.88±0.3, 19.12±0.3, 19.32±0.3, 20.73±0.3, 22.33±0.3, 24.37±0.3, 27.19±0.3, and 27.69±0.3 degrees 2-θ. A crystalline microporous germanosilicate CIT-14/IST composition according to claim 1, having a Si:Ge ratio ranging from 2:1 to 20:1. 2. The crystalline microporous germanosilicate CIT-14/IST composition of claim 1, which consists of orthorhombic crystals. 4. The crystalline microporous germanosilicate CIT-14/IST composition according to claim 3, characterized in that it has a Cmmm space group, or a Cmcm space group, or an intracrystalline disorder of both domains. 4. The crystalline microporous germanosilicate CIT-14/IST composition of claim 3, wherein the crystals have unit cell parameters according to:
[Table 1] 2. The crystalline microporous germanosilicate CIT- of claim 1, wherein the 8-membered ring channel has a pore size of about 3.3 Å x 3.9 Å and the 12-membered ring channel has a pore size of about 4.9 Å x 6.4 Å. 14/IST composition. 2. The crystalline microporous germanosilicate CIT-14/IST composition of claim 1, which is substantially free of fluoride. The crystalline microporous germanosilicate CIT- of claim 1, having micropores optionally containing alkali metal cation salts, alkaline earth metal salts, transition metals, transition metal oxides, transition metal salts, or combinations thereof. 14/IST composition. 6.45±0.2, 7.18±0.2, 12.85±0.2, 20.78±0.2, 26.01±0.2 and 26.68±, which are fluoride-free and have a three-dimensional framework with pores defined by 10- and 14-membered rings A crystalline microporous germanosilicate designated CIT-13/OH that exhibits powder X-ray diffraction (XRD) with at least 5 peaks at 0.2 degrees 2-theta. The crystalline microporous germanosilicate CIT-13/OH according to claim 9, having a Si:Ge ratio in the range of 3.5-5.2. 10. The crystalline microporous germanosilicate CIT-13/OH of Claim 9, wherein the d4r units consist of an average of at least 4 Ge atoms per d4r unit, allowing for the presence of Ge-4-rings in the d4r units. The crystalline microporous germanosilicate CIT- of claim 9, having micropores optionally containing alkali metal cation salts, alkaline earth metal salts, transition metals, transition metal oxides, transition metal salts, or combinations thereof. 13/OH composition. 10. A method of preparing the crystalline microporous germanosilicate CIT-13/OH of claim 9, said method comprising hydrothermally treating an aqueous composition obtained from a mixture of:
(a) It is a source of silicon oxide ( _SiO2 ).
(b) a source of germanium oxide ( _GeO2 ); and
(c) be any source of aluminum oxide, boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combinations or mixtures thereof;
(d) at least one hydroxide salt of a substituted benzylimidazolium organic structure director (OSDA) cation having the structure:
[Chemical 1]
(e) optionally, at least one compositionally matched seed crystal; and
(f) water.
under conditions effective to crystallize a crystalline microporous germanosilicate composition designated CIT-13/OH;
(a) Si:Ge molar ratio in the range of 2 to 4, preferably 2.
(b) Water with a water:Si molar ratio in the range of 8:1 to 12:1.
(c) water having a molar ratio of water:(SiO ₂ +GeO ₂ ) in the range of 6:1 to 7:1;
(c) containing hydroxide ions (OH) in a molar ratio of OH:(SiO ₂ +GeO ₂ ) in the range of about 0.3:1 to 0.7:1;
Here, the aqueous composition is essentially free of fluoride ions. A process for preparing the crystalline microporous germanosilicate CIT-14/IST of claim 1, wherein the crystalline microporous germanosilicate CIT-13/OH of claim 9 is mixed with a concentrated strong aqueous mineral acid at a high temperature at an intermediate contacting for a time sufficient to form the microporous germanosilicate "-CIT-14". 14. The method of claim 13, wherein (a) the mineral acid is aqueous HCl or _HNO3 ; (b) the concentration of the strong aqueous mineral acid ranges from 6 to 12M; (c) the temperature rise is 80 ^° C. and/or (d) the sufficient time is in the ^range of 4 to 24 hours. The intermediate microporous germanosilicate "-CIT-14" is isolated, the "-CIT-14" material is washed with water until the wash is pH neutral, and then the isolated and washed "-CIT-14" material is -14" material, further comprising heating the material to a temperature in the range of about 450 ^° C to 650 ^° C for a time in the range of 2 hours to 12 hours. Use of the crystalline microporous germanosilicate CIT-14/IST composition of claim 8 or the crystalline microporous germanosilicate CIT-13/OH composition of claim 12 as a catalyst or vehicle for gas separation. (a) Carbonylation of dimethyl ether (DME) with CO at low temperature.
(b) reducing NOx with methane;
(c) cracking, hydrocracking, or dehydrogenating hydrocarbons;
(d) degreasing the hydrocarbon feedstock;
(e) converting paraffins to aromatics;
(f) isomerizing or heterogenizing the aromatic feedstock;
(g) alkylating the aromatic hydrocarbon;
(h) oligomerizing the alkene.
(i) aminate a lower alcohol;
(j) separating and sorbing lower alkanes from the hydrocarbon feedstock;
(k) isomerizing olefins;
(l) producing high molecular weight hydrocarbons from low molecular weight hydrocarbons;
(m) reforming hydrocarbons;
(n) conversion of lower alcohols or other oxygen-containing hydrocarbons to produce olefinic products, including methanol to olefinic processes;
(o) epoxidizing the olefin with hydrogen peroxide;
(p) reducing the content of oxides of nitrogen in the gas stream in the presence of oxygen;
(q) separating nitrogen from a nitrogen-containing gas mixture, or
(r) converting synthesis gas containing hydrogen and carbon monoxide into a hydrocarbon stream, or
(s) first by contacting each raw material with the crystalline microporous germanosilicate CIT-14/IST composition of claim 8 or the crystalline microporous germanosilicate CIT-13/OH composition of claim 12; reducing the concentration of organic halides in the hydrocarbon products of
process including.

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